US8871403B2 - Fuel cell stack system, channel structure, fuel cell, electrode and electronic device - Google Patents

Fuel cell stack system, channel structure, fuel cell, electrode and electronic device Download PDF

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US8871403B2
US8871403B2 US12/671,598 US67159808A US8871403B2 US 8871403 B2 US8871403 B2 US 8871403B2 US 67159808 A US67159808 A US 67159808A US 8871403 B2 US8871403 B2 US 8871403B2
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fuel
fuel cell
channel
electrolytic solution
electrode
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US20110223496A1 (en
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Kengo Makita
Shinichi Uesaka
Yasunori Ohto
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Murata Manufacturing Co Ltd
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Sony Corp
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Priority claimed from JP2007202006A external-priority patent/JP5182473B2/ja
Priority claimed from JP2007216397A external-priority patent/JP5182475B2/ja
Priority claimed from JP2007231562A external-priority patent/JP4952453B2/ja
Priority claimed from JP2007236647A external-priority patent/JP5182476B2/ja
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/18—Regenerative fuel cells, e.g. redox flow batteries or secondary fuel cells
    • H01M8/184—Regeneration by electrochemical means
    • H01M8/188—Regeneration by electrochemical means by recharging of redox couples containing fluids; Redox flow type batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/8605—Porous electrodes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/02—Details
    • H01M8/0202—Collectors; Separators, e.g. bipolar separators; Interconnectors
    • H01M8/0247—Collectors; Separators, e.g. bipolar separators; Interconnectors characterised by the form
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/02—Details
    • H01M8/0202—Collectors; Separators, e.g. bipolar separators; Interconnectors
    • H01M8/0258—Collectors; Separators, e.g. bipolar separators; Interconnectors characterised by the configuration of channels, e.g. by the flow field of the reactant or coolant
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/04—Auxiliary arrangements, e.g. for control of pressure or for circulation of fluids
    • H01M8/04298—Processes for controlling fuel cells or fuel cell systems
    • H01M8/04313—Processes for controlling fuel cells or fuel cell systems characterised by the detection or assessment of variables; characterised by the detection or assessment of failure or abnormal function
    • H01M8/04537—Electric variables
    • H01M8/04544—Voltage
    • H01M8/04559—Voltage of fuel cell stacks
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/04—Auxiliary arrangements, e.g. for control of pressure or for circulation of fluids
    • H01M8/04298—Processes for controlling fuel cells or fuel cell systems
    • H01M8/04313—Processes for controlling fuel cells or fuel cell systems characterised by the detection or assessment of variables; characterised by the detection or assessment of failure or abnormal function
    • H01M8/04537—Electric variables
    • H01M8/04574—Current
    • H01M8/04589—Current of fuel cell stacks
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/04—Auxiliary arrangements, e.g. for control of pressure or for circulation of fluids
    • H01M8/04298—Processes for controlling fuel cells or fuel cell systems
    • H01M8/04694—Processes for controlling fuel cells or fuel cell systems characterised by variables to be controlled
    • H01M8/04746—Pressure; Flow
    • H01M8/04753—Pressure; Flow of fuel cell reactants
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/04—Auxiliary arrangements, e.g. for control of pressure or for circulation of fluids
    • H01M8/04298—Processes for controlling fuel cells or fuel cell systems
    • H01M8/04694—Processes for controlling fuel cells or fuel cell systems characterised by variables to be controlled
    • H01M8/04791—Concentration; Density
    • H01M8/0482—Concentration; Density of the electrolyte
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/24—Grouping of fuel cells, e.g. stacking of fuel cells
    • H01M8/249—Grouping of fuel cells, e.g. stacking of fuel cells comprising two or more groupings of fuel cells, e.g. modular assemblies
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/50—Fuel cells
    • Y02E60/528—
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T137/00—Fluid handling
    • Y10T137/8593—Systems
    • Y10T137/87265—Dividing into parallel flow paths with recombining

Definitions

  • the present disclosure relates to a fuel cell stack system such as a direct methanol fuel cell (DMFC) directly supplying methanol to a fuel electrode to cause a reaction, a fuel cell, an electrode used in the fuel cell, and an electronic device using them.
  • a fuel cell stack system such as a direct methanol fuel cell (DMFC) directly supplying methanol to a fuel electrode to cause a reaction, a fuel cell, an electrode used in the fuel cell, and an electronic device using them.
  • a channel structure allowing a fluid (a liquid or a gas) to flow therethrough, a fuel cell such as a DMFC using the channel structure, and an electronic device including them.
  • the present invention relates to a channel structure suitable for a micro TAS (Total Analysis System), a fuel cell or the like.
  • TAS Total Analysis System
  • Indicators of characteristics of a battery include energy density and output density.
  • the energy density is an amount of energy storage of the battery per unit mass
  • the output density is an output amount of the battery per unit mass.
  • Lithium-ion secondary batteries combine two characteristics of relatively high energy density and remarkably high output density, and also have high perfection, so it is widely adopted as power sources for mobile devices.
  • the mobile devices tend to consume more power with performance enhancement, thereby further improvements in energy density and output density of the lithium-ion secondary batteries are desired.
  • Solutions to such an issue include changing an electrode material forming a cathode and an anode, improving a method of applying an electrode material, improving a method of sealing an electrode material, and the like, and research aimed at improving the energy density of the lithium-ion secondary batteries has been conducted.
  • a hurdle to practical use is still high.
  • constituent materials used for the lithium-ion secondary batteries are changed, it is difficult to expect a drastic improvement in the energy density.
  • the fuel cell has a configuration in which an electrolyte is arranged between an anode (a fuel electrode) and a cathode (an oxygen electrode), and a fuel, and air or oxygen are supplied to the fuel electrode and the oxygen electrode, respectively.
  • an oxidation-reduction reaction in which the fuel is oxidized by oxygen occurs in the fuel electrode and the oxygen electrode, and a part of chemical energy of the fuel is converted into electrical energy to be extracted.
  • AFC alkaline fuel cell
  • PAFC phosphoric acid fuel cell
  • MCFC molten carbonate fuel cell
  • SOFC solid electrolyte fuel cell
  • PEFC polymer electrolyte fuel cell
  • the fuel for the fuel cells various flammable substances such as hydrogen and methanol may be used.
  • a gas fuel such as hydrogen is necessary to be stored in a storage cylinder, so the gas fuel is not suitable to size reduction.
  • a liquid fuel such as methanol is advantageous in terms of easy storage.
  • the DMFC does not need a reformer for extracting hydrogen from the fuel, so the DMFC has advantages that its configuration is simplified and its size is easily reduced.
  • methanol as the fuel is typically supplied to the fuel electrode as a high- or low-concentrated aqueous solution or as gaseous pure methanol, and methanol is oxidized to carbon dioxide in a catalyst layer of the fuel electrode. Protons produced at this time move to the oxygen electrode through an electrolyte film separating the fuel electrode and the oxygen electrode, and then react with oxygen in the oxygen electrode, thereby to generate water. Reactions occurring in the fuel electrode, the oxygen electrode and the whole DMFC are represented by Chemical Formula 1.
  • the energy density of methanol as the fuel for the DMFC is theoretically 4.8 kW/L, which is 10 or more times larger than the energy density of a typical lithium-ion secondary battery. That is, the fuel cell using methanol as a fuel has a good chance of exceeding the energy density of the lithium-ion secondary battery. Therefore, among various fuel cells, the DMFC is the most likely to be used as an energy source for a mobile device, an electric vehicle or the like.
  • the DMFC has such an issue that even though its theoretical voltage is 1.23 V, its output voltage when actually generating electric power is reduced to approximately 0.6 V or less.
  • a cause of a reduction in output voltage is a voltage drop caused by internal resistance of the DMFC, and the DMFC has internal resistance such as resistance accompanied with reactions occurring in both electrodes, resistance accompanied with movement of a substance, resistance generated when protons moves through the electrolyte film and further, contact resistance.
  • Energy which is allowed to be actually extracted as electrical energy through oxidation of methanol is represented by a product of an output voltage during electric power generation and the quantity of electric power flowing through a circuit, so when the output voltage during electric power generation is reduced, the energy which is allowed to be actually extracted is reduced correspondingly.
  • the quantity of electric power which is allowed to be extracted to the circuit through oxidation of methanol is proportional to the amount of methanol in the DMFC.
  • Methanol crossover is a phenomenon in which methanol reaches the oxygen electrode side from the fuel electrode side through the electrolyte film due to two mechanisms of a phenomenon in which methanol diffusively moves by a difference in methanol concentration between the fuel electrode side and the oxygen electrode side and an electroosmotic phenomenon in which hydrated methanol is transported by the movement of water caused by the movement of protons.
  • methanol having passed through the electrolyte film is oxidized in a catalyst layer of the oxygen electrode.
  • an oxidation reaction of methanol on the oxygen electrode side is the same as the above-described oxidation reaction on the fuel electrode side, the oxidation reaction on the oxygen electrode side causes a reduction in the output voltage of the DMFC.
  • methanol is not used for electric power generation on the fuel electrode side, and is wasted on the oxygen electrode side, so the quantity of electric power which is allowed to be extracted to the circuit is reduced correspondingly.
  • the catalyst layer of the oxygen electrode is not a platinum (Pt)-ruthenium (Ru) alloy catalyst but a platinum (Pt) catalyst, so there is such an inconvenience that carbon monoxide (CO) is easily absorbed onto a surface of the catalyst to cause catalyst poisoning.
  • the DMFC has two issues of a reduction in voltage caused by internal resistance and methanol crossover and fuel waste caused by methanol crossover, and these issues cause a decline in electric power generation efficiency of the DMFC. Therefore, to improve the electric power generation efficiency of the DMFC, research and development aimed at improving characteristics of materials forming the DMFC, and research and development aimed at optimizing operating conditions of the DMFC have been intensely conducted.
  • the research aimed at improving the characteristics of the materials forming the DMFC includes research related to the electrolyte film and a catalyst on the fuel electrode side.
  • a polyperfluoroalkyl sulfonic acid-based resin film (“Nafion (a registered trademark)” manufactured by E. I. du Pont de Nemours and Company) is typically used; however, as an electrolyte film having higher proton conductivity and a higher ability to prevent methanol from passing through than the polyperfluoroalkyl sulfonic acid-based resin film, a fluoropolymer film, a hydrocarbon-based polymer electrolyte film or a hydrogel-based electrolyte film and the like have been studied.
  • the catalyst on the fuel electrode side research and development of a catalyst having higher activity than a platinum (Pt)-ruthenium (Ru) alloy catalyst which is typically used at present have been conducted.
  • Japanese Unexamined Patent Application Publication No. S59-191265 discloses a fuel cell using a liquid electrolyte (an electrolytic solution) and not needing the electrolyte film.
  • the electrolytic solution may remain stationary between the oxygen electrode and the fuel electrode, or the electrolytic solution may circulate by flowing through a channel arranged between the oxygen electrode and the fuel electrode to outside, and then going back to the channel.
  • the fuel cell has issues that it is more difficult to manufacture the fuel cell than a fuel cell including a solid electrolyte film in related art, and it is difficult to stably generate electric power.
  • the fluid is sent to a main channel connected to all fuel cell elements so as to be supplied to each of the fuel cell elements through the channel. That is, the fluid is supplied by parallel connection.
  • the fluid is supplied by parallel connection.
  • it is extremely difficult to supply the fluid uniformly to each of the fuel cell elements.
  • Japanese Unexamined Patent Application Publication No. 2006-164872 discloses that a fluid is supplied to each fuel cell element through an individual pump and a valve.
  • a fluid is supplied to each fuel cell element through an individual pump and a valve.
  • devices for supply such as pumps occupy a majority of the fuel cell stack system to cause an increase in size of the fuel cell stack system, so the configuration is extremely unrealistic.
  • the channel of the fuel cell there are a large number of kinds such as a serpentine (meandering) shape type as one kind of a serial channel in which an inlet 352 A and an outlet 353 A are connected by one channel 356 A as illustrated in FIG. 41 and a grid type in which a grid-like channel 356 B is arranged in a matrix form between the inlet 352 A and the outlet 353 A as illustrated in FIG. 42 .
  • a serpentine (meandering) shape type as one kind of a serial channel in which an inlet 352 A and an outlet 353 A are connected by one channel 356 A as illustrated in FIG. 41
  • a grid type in which a grid-like channel 356 B is arranged in a matrix form between the inlet 352 A and the outlet 353 A as illustrated in FIG. 42 .
  • the serpentine type channel shape has a major issue.
  • the concentration distribution of a reactive gas or a liquid tends to be generated in the channel and electric power is generated locally under a high utilization rate condition and a low utilization rate condition often occurs, thereby the case tends to become a cause of reductions in the performance and longevity of the fuel cell. That is, the concentration distribution or the like causes catalyst deterioration, thereby to reduce its performance not temporarily but permanently.
  • the introduction of a parallel channel is considered.
  • the parallel channel as illustrated in FIG. 43 , first, the fluid flows from the inlet 352 A to a first main channel 352 to be supplied to a plurality of parallel channels 354 connected to the first main channel 352 at a right angle, and then the fluid joins into a second main channel 353 connected to the exit 353 A.
  • the pressure loss is allowed to be significantly reduced.
  • the fuel electrode and the oxygen electrode is constantly in contact with the fluid, so there is an issue that deterioration in the electrodes such as a crack or a hole is inevitable.
  • the deterioration in the fuel electrode promotes fuel crossover, and the deterioration in the oxygen electrode causes leakage of the electrolytic solution.
  • Such deterioration in the electrodes is fatal, and the characteristics of the fuel cell are pronouncedly deteriorated.
  • a fine channel formed on a glass substrate or a base such as a plastic film is used as an analyzer, a chemical reaction chip or a biochemistry chip or the like.
  • a fluid connector tube
  • an extendable member 422 is arranged on an inlet-outlet 431 of a channel 420 , and a gap 440 between the inlet-outlet 421 and a fluid connector 430 is filled with the extendable member 422 .
  • Japanese Unexamined Patent Application Publication No. 2004-58214 discloses that a connection section having adhesion which is fixable to another device is arranged around an opening of a channel.
  • a tube is connected in a direction perpendicular to a surface of the base, so a space in a vertical direction of the base is occupied by connection of the fluid connector, thereby the bases to which the fluid connectors are connected are not allowed to be stacked in parallel.
  • the thickness of the base and the thickness of the tube diameter of the fluid connector connected to the base are substantially equal to each other, and the fluid connector is connected to a side surface of the base with an adhesive or the like; however, in addition to needing care for adhesion, the fluid connector is not allowed to be connected to a substrate with a smaller thickness than the tube diameter (outside diameter) of the fluid connector.
  • a first object is to provide a fuel cell stack system allowing a fuel or an electrolytic solution to be supplied uniformly to each fuel cell element with a simple configuration, and an electronic device using the fuel cell stack system.
  • a second object is to provide a channel structure allowing a fluid to flow uniformly through parallel channels, and a fuel cell using the channel structure, and an electronic device including them.
  • a third object is to provide a fuel cell allowed to prevent deterioration of a fuel electrode or an oxygen electrode, an electrode, and an electronic device using the electrode.
  • a fourth object is to provide a channel structure allowed to reduce a space for connection of a fluid connector.
  • a fuel cell stack system includes a plurality of fuel cell elements, in which the plurality of fuel cell elements each include a fuel electrode and an oxygen electrode which are arranged so as to face each other, and a channel allowing at least an electrolytic solution to flow therethrough, and the channels of some or all of the plurality of fuel cell elements are connected in series to one another.
  • connection in series means that an outlet of the fuel channel or the electrolytic solution channel of one fuel cell element is connected to an inlet of the fuel channel or the electrolytic solution channel of the next fuel cell element.
  • connected in parallel means that there is a main channel connected to all of the fuel cell elements, and the main channel is divergently connected to an inlet of the fuel channel or the electrolytic solution channel of each fuel cell element.
  • the channels of some or all of the plurality of fuel cell elements are connected in series to one another, so the number of supply auxiliaries such as pumps or valves is reduced, thereby the configuration is simplified. Moreover, influences such as nonuniformity of the flow of fluid through each of the fuel cell elements, a change in pressure loss, internal characteristics and the like are reduced, and the fuel or the electrolytic solution is uniformly supplied to each of the fuel cell elements. Therefore, stability of electric power supply is improved.
  • a first electronic device includes a fuel cell stack system including a plurality of fuel cell elements, and the fuel cell stack system is configured of the above-described fuel cell stack system of the invention.
  • the fuel cell stack system according to the above-described embodiment allowing stable electric power generation is included, so even if the number of fuel cell elements is increased, stable electric power generation is allowed, and the first electronic device is allowed to respond to more functions and higher performance with an increase in electric power consumption.
  • a first channel structure includes a first main channel connected to a main inlet for fluid; a second main channel connected to a main outlet for fluid; and two or more parallel channels arranged between the first main channel and the second main channel and each having an inlet connected to the first main channel and an outlet connected to the second main channel, in which one or more of the two or more parallel channels each include a region of which the sectional area is reduced at either or both of the inlet and the outlet.
  • a fluid enters from the main inlet to the first main channel, and then enters from the first main channel to the inlets of the parallel channels to flow through the parallel channels, and the fluid enters from the outlets of the parallel channels to the second main channel to exit from a main outlet.
  • the region of which the sectional area is reduced is arranged at either or both of the inlet and the outlet of one or more of the parallel channels, so the region becomes a barrier to the flow of the fluid, and the resistance of the first main channel or the second main channel to the flow is reduced to cause easy flow of the fluid, and uniformity of the flow of the fluid through the parallel channels is improved.
  • a first fuel cell of an embodiment including an electrolyte between a fuel electrode and an oxygen electrode includes: a fuel channel allowing a fluid including a fuel to flow therethrough on a side opposite to a side where the oxygen electrode is arranged of the fuel electrode, in which the fuel channel includes a first main channel connected to a main inlet for the fluid, a second main channel connected to a main outlet for the fluid; and two or more parallel channels arranged between the first main channel and the second main channel and each having an inlet connected to the first main channel and an outlet connected to the second main channel, and one or more of the two or more parallel channels each include a region of which the sectional area is reduced at either or both of the inlet and the outlet.
  • the channel structure according to the above-described embodiment is included as the fuel channel, so the fluid including the fuel uniformly flows through the parallel channels. Therefore, when the number of parallel channels is increased, an output is increased with a linear relationship, and electric power characteristics are improved.
  • a second electronic device of the embodiment includes a fuel cell including an electrolyte between a fuel electrode and an oxygen electrode, and the fuel cell is configured of the above-described first fuel cell of the embodiment.
  • the fuel cell of the embodiment with improved electric power generation characteristics is included, so the second electronic device is allowed to respond to more functions and higher performance with an increase in electric power consumption.
  • a second fuel cell includes an electrolytic solution between a fuel electrode and an oxygen electrode, in which either or both of the fuel electrode and the oxygen electrode include a catalyst layer and a functional layer arranged on the catalyst layer and preventing direct contact between the catalyst layer and the electrolytic solution.
  • An electrode according to the embodiment is used as a fuel electrode or an oxygen electrode of a fuel cell including an electrolytic solution between the fuel electrode and the oxygen electrode, and includes a catalyst layer; and a functional layer arranged on the catalyst layer and preventing direct contact between the catalyst layer and the electrolytic solution.
  • a third electronic device includes a fuel cell including an electrolytic solution between a fuel electrode and an oxygen electrode, and the fuel cell is configured of the above-described second fuel cell of the invention.
  • the functional layer preventing direct contact between the catalyst layer and the electrolytic solution is arranged on the catalyst layer, the occurrence of deterioration such as a crack or a hole in the fuel electrode or the oxygen electrode is prevented. Therefore, fuel crossover due to deterioration of the fuel electrode, the leakage of the electrolytic solution due to the deterioration of the oxygen electrode, and the like is reduced, and stable characteristics are maintained, and long-time electric power generation is allowed.
  • the second fuel cell according to the above-described embodiment allowed to generate electric power for a long time is included, so the third electronic device is allowed to respond to more functions and higher performance with an increase in electric power consumption.
  • a second channel structure of the embodiment includes a channel for fluid formed in a base; and a fluid connector connected to the channel in a direction parallel to a main surface of the base.
  • “main surface of the base” is a flat surface in the case where the base is a thin plate made of glass, silicon (Si) or the like, but is not necessarily a flat surface, and, for example, in the case where the base is configured of a flexible film, the main surface may be a flat surface or a curved surface.
  • the channels of some or all of the plurality of fuel cell elements are connected in series to one another, so the number of supply arbitraries such as pumps or valves is allowed to be reduced, and the configuration is allowed to be simplified. Moreover, influences such as nonuniformity of the flow of fluid through each of the fuel cell elements, a change in pressure loss, and internal characteristics are allowed to be reduced, and the fuel or the electrolytic solution is allowed to be uniformly supplied to each of the fuel cell elements. Therefore, the stability of electric power generation is allowed to be improved, and the fuel cell stack system is suitable for a multifunctional high-performance electronic device consuming a large amount of electric power.
  • the region of which the sectional area is reduced is arranged at either or both of the inlet and the outlet of one or more of two or more parallel channels, so the fluid is allowed to uniformly flow through the parallel channels. Therefore, when the channel structure is applied to a fuel channel of a fuel cell, or the like, the fluid including the fuel is allowed to uniformly flow through the parallel channels, and electric power characteristics are allowed to be improved, and the fuel channel is suitable for a multifunctional high-performance electronic device consuming a large amount of electric power.
  • the functional layer preventing direct contact between the catalyst layer and the electrolytic solution is arranged on the catalyst layer, deterioration such as a crack or a hole in the fuel electrode or the oxygen electrode is preventable. Therefore, a decline in characteristics of the fuel cell is preventable, and long-time electric power generation is allowed, and they are suitable for a multifunctional high-performance electronic device consuming a large amount of electric power.
  • the fluid connector is connected to the channel formed in the base in a direction parallel to the main surface of the base, so a space in a vertical direction of the base is not occupied by connection of the fluid connector. Therefore, a space for connection of the fluid connector is allowed to be reduced, and the bases where the fluid connector is connected are allowed to be stacked in parallel, thereby integration is allowed to be improved.
  • FIG. 1 is an illustration of a schematic configuration of an electronic device including a fuel cell stack system according to a first embodiment.
  • FIG. 2 is an illustration of configurations of two fuel cell elements in a fuel cell stack system illustrated in FIG. 1 .
  • FIG. 3 is an illustration of another connection example of an electrolyte channel and a fuel channel.
  • FIG. 4 is an illustration of still another connection example of the electrolyte channel and the fuel channel.
  • FIG. 5 is an illustration of a further connection example of the electrolyte channel and the fuel channel.
  • FIG. 6 is an illustration of a still further connection example of the electrolyte channel and the fuel channel.
  • FIG. 7 is an illustration of a still connection example of the electrolyte channel and the fuel channel.
  • FIG. 8 is an illustration of a schematic configuration of an electronic device including a fuel cell system according to a second embodiment.
  • FIG. 9 is a sectional view illustrating a configuration of a fuel cell illustrated in FIG. 8 .
  • FIG. 10 is a perspective view illustrating an outer appearance of a fuel channel illustrated in FIG. 9 .
  • FIG. 11(A) is a plan view illustrating a configuration of the fuel channel illustrated in FIG. 10 when viewed from a side where a first main channel, a second main channel and parallel channels are arranged
  • FIG. 11(B) is a sectional view taken along a line XIB-XIB of FIG. 11(A)
  • FIG. 11(C) is a sectional view illustrating a configuration of a rib in one parallel channel.
  • FIG. 12 is a perspective view illustrating an outer appearance of an electrolytic solution channel illustrated in FIG. 9 .
  • FIG. 13(A) illustrates a configuration of the electrolyte channel illustrated in FIG. 12 when viewed from a side where a first main channel, a second main channel and parallel channels are arranged
  • FIG. 13(B) is a sectional view taken along a line XIIIB-XIIIB of FIG. 13(A)
  • FIG. 13(C) is a sectional view illustrating a configuration of a rib in one parallel channel.
  • FIG. 14 is an illustration of a configuration of a fuel cell of a fuel cell system according to a third embodiment.
  • FIG. 15 is an illustration of a modification example of the fuel cell illustrated in FIG. 14 .
  • FIG. 16 is an illustration of another modification example of the fuel cell illustrated in FIG. 14 .
  • FIG. 17 is an illustration of a configuration of a fuel cell according to a fourth embodiment.
  • FIG. 18 is a sectional view illustrating a configuration of a channel structure according to a fifth embodiment.
  • FIG. 19 is a plan view illustrating a configuration of the channel structure illustrated in FIG. 18 .
  • FIG. 20 is a perspective view illustrating an example of an exploded configuration of the channel structure illustrated in FIGS. 18 and 19 .
  • FIG. 21 is a perspective view illustrating another example of the exploded configuration of the channel structure illustrated in FIGS. 18 and 19 .
  • FIG. 22 is a sectional view illustrating a configuration of a channel structure according to a modification example of the embodiment.
  • FIG. 23 is an exploded perspective view illustrating a configuration of an auxiliary component illustrated in FIG. 22 .
  • FIG. 24 is a sectional view illustrating a configuration of a fuel cell in which a fuel channel is configured of the channel structure illustrated in FIGS. 18 and 19 .
  • FIG. 25 is a sectional view illustrating a configuration of a fuel cell in which a fuel channel and an electrolytic solution channel each are configured of the channel structure illustrated in FIGS. 18 and 19 .
  • FIG. 26 is a plot illustrating results of Example 1.
  • FIG. 27 is a plot illustrating results of Example 1.
  • FIG. 28 is a plot illustrating results of Example 2.
  • FIG. 29 is a plot illustrating results of Example 3.
  • FIG. 30 is a plot illustrating a result of Comparative Example 1.
  • FIG. 31 is a plot illustrating a result of Example 4.
  • FIG. 32 is a plot illustrating a result of Comparative Example 2.
  • FIG. 33 is a plot illustrating a result of Example 5.
  • FIG. 34 is an illustration of configurations of two fuel cell elements of a fuel cell stack system according to a modification example.
  • FIG. 35 is an illustration of configurations of two fuel cell elements of the fuel cell stack system according to a modification example.
  • FIG. 36 is a plan view and a sectional view illustrating a modification example of the fuel channel illustrated in FIG. 11 .
  • FIG. 37 is a plan view and a sectional view illustrating another modification example of the fuel channel illustrated in FIG. 11 .
  • FIG. 38 is a sectional view illustrating a modification example of the rib illustrated in FIG. 11(C) .
  • FIG. 39 is a sectional view illustrating a modification example of the fuel cell illustrated in FIG. 9 .
  • FIG. 40 is a sectional view illustrating another modification example of the fuel cell illustrated in FIG. 9 .
  • FIG. 41 is a plan view illustrating an example of a channel in related art.
  • FIG. 42 is a plan view illustrating another example of the channel in related art.
  • FIG. 43 is a plan view illustrating still another example of the channel in related art.
  • FIG. 44 is an illustration for describing a method of connecting a fluid connected to the channel in related art.
  • FIG. 1 illustrates a schematic configuration of an electronic device including a fuel cell stack system according to a first embodiment.
  • the electronic device is a small- to large-sized device needing electric power, for example, a mobile device such as a cellular phone or a PDA (Personal Digital Assistant), a notebook PC (Personal Computer), a camera, or a vehicle, and the electronic device includes a fuel cell stack system 1 and an external circuit (load) 2 driven by electrical energy generated in the fuel cell stack system 1 .
  • a mobile device such as a cellular phone or a PDA (Personal Digital Assistant), a notebook PC (Personal Computer), a camera, or a vehicle
  • the electronic device includes a fuel cell stack system 1 and an external circuit (load) 2 driven by electrical energy generated in the fuel cell stack system 1 .
  • load load
  • the fuel cell stack system 1 includes, for example, a fuel cell stack 110 , a measurement section 120 measuring the operating state of the fuel cell stack 110 , and a control section 130 determining operating conditions of the fuel cell stack 110 based on a measurement result by the measurement section 120 .
  • the fuel cell stack system 1 also includes, for example, an electrolyte supply section 140 supplying, for example, a sulfuric acid as an electrolytic solution F 1 to the fuel cell stack 110 , and a fuel supply section 140 supplying, for example, methanol as a fuel F 2 to the fuel cell stack 110 .
  • electrolyte film When the electrolyte is supplied as a fluid in such a manner, an electrolyte film is not necessary, and electric power is allowed to be generated without influences of temperature and humidity, and compared to a typical fuel cell using the electrolyte film, ionic conductivity (proton conductivity) is allowed to be improved. Moreover, risks such as deterioration of the electrolyte film or a decline in proton conductivity caused by dryness of the electrolyte film are eliminated, and issues such as flooding and moisture control in an oxygen electrode are solvable.
  • the fuel cell stack 110 is configured by stacking a plurality of (for example, four in FIG. 1 ) fuel cell elements 111 in a vertical direction (a stacking direction).
  • FIG. 2 illustrates configurations of two fuel cell elements 111 ( 111 A and 111 B) of the fuel cell stack 110 illustrated in FIG. 1 .
  • the fuel cell elements 111 are so-called direct methanol flow based fuel cells (DMFFC), and each have a configuration in which a fuel electrode (anode) 10 and an oxygen electrode (cathode) 20 are arranged so as to face each other.
  • An electrolytic solution channel 30 allowing the electrolytic solution F 1 to flow therethrough is arranged between the fuel electrode 10 and the oxygen electrode 20 .
  • a fuel channel 40 allowing the fuel F 2 to flow therethrough is arranged on the outside of the fuel electrode 10 , that is, a side opposite to a side where the oxygen electrode 20 is arranged.
  • the fuel electrode 10 has a configuration in which a catalyst layer 11 , a diffusion layer 12 and a current collector 13 are stacked in order from the oxygen electrode 2 side, and is contained in an external member 14 . Moreover, the fuel electrode 10 also has a function as a separation film separating the electrolytic solution F 1 and the fuel F 2 , and is allowed to prevent crossover so as to obtain high energy density.
  • the oxygen electrode 20 has a configuration in which a catalyst layer 21 , a diffusion layer 22 and a current collector 23 are stacked in order from the fuel electrode side, and is contained in an external member 24 . In addition, air, that is, oxygen is supplied to the oxygen electrode 20 through the external member 24 .
  • the catalyst layers 11 and 21 are made of, for example, a simple substance or an alloy of metal such as palladium (Pd), platinum (Pt), iridium (Ir), rhodium (Rh), ruthenium (Ru) or the like as a catalyst.
  • the catalyst layers 11 and 21 may include a proton conductor or a binder in addition to the catalyst.
  • the proton conductor the above-described polyperfluoroalkyl sulfonic acid-based resin (“Nafion (a registered trademark)” manufactured by E. I. du Pont de Nemours and Company) or other resins having proton conductivity are cited.
  • the binder is added to maintain the strength or flexibility of the catalyst layers 11 and 21 , and as the binder, for example, a resin such as polytetrafluoroethylene (PTFE) or polyvinylidene fluoride (PVDF) is cited.
  • a resin such as polytetrafluoroethylene (PTFE) or polyvinylidene fluoride (PVDF) is cited.
  • the diffusion layers 12 and 22 are configured of, for example, a carbon cloth, a carbon paper or a carbon sheet.
  • the diffusion layers 12 and 22 are preferably subjected to water-repellent treatment by polytetrafluoroehylene (PTFE).
  • PTFE polytetrafluoroehylene
  • the current collectors 13 and 23 are configured of, for example, a titanium (Ti) mesh.
  • the external members 14 and 24 have, for example, a thickness of 2.0 mm, and are made of a commonly available material such as a titanium (Ti) plate or an acid-resistant metal plate, but the material is not specifically limited thereto.
  • the external members 14 and 24 are preferably as thin a thickness as possible.
  • the electrolytic solution channel 30 and the fuel channel 40 are, for example, fine channels formed by processing a resin sheet, and are adhered to the fuel electrode 10 .
  • the number of the channels is not limited.
  • the widths, heights and lengths of the channels are not specifically limited, but they are preferably small.
  • the electrolytic solution channels 30 and the fuel channels 40 of all of four fuel cell elements 111 are connected in series to one another. Thereby, in the fuel cell stack system 1 , the fuel F 2 or the electrolytic solution F 1 is allowed to be uniformly supplied to each of the fuel cell elements 111 with a simple configuration.
  • an electrolytic solution inlet 24 A and an electrolytic solution outlet 24 B are arranged in the external member 24 .
  • the electrolytic solution inlet 24 A of a first fuel cell element 111 A is connected to an electrolytic solution supply section 140 (not illustrated in FIG. 2 , refer to FIG. 1 ), and the electrolytic solution outlet 24 B is connected to the electrolytic solution inlet 24 A of the next fuel cell element 111 B through a connection channel 24 C.
  • the electrolytic solution inlet 24 A of the first fuel cell element 111 and the electrolytic solution outlet 24 B of a last fuel cell element 111 are connected to the electrolytic solution supply section 140 , and the electrolytic solution inlet 24 A of each of other fuel cell elements 111 is connected to the electrolytic solution outlet 24 B of a fuel cell element 111 previous thereto.
  • the electrolytic solution channels 30 of all fuel cell elements 111 are connected in series to one another, and the electrolytic solution F 1 supplied from the electrolytic solution supply section 140 enters the electrolytic solution inlet 24 A of the first fuel cell element 111 A, and exits from the electrolytic solution outlet 24 B of the first fuel cell element 111 A to enter the electrolytic solution inlet 24 A of the next fuel cell element 111 B, and after the electrolytic solution F 1 flows through all of the fuel cell elements 111 in the same manner, the electrolytic solution F 1 exits from the electrolytic solution outlet 24 B of the last fuel cell element 111 to return to the electrolytic solution supply section 140 .
  • a fuel inlet 14 A and a fuel outlet 14 B are arranged in the external member 14 .
  • the fuel inlet 14 A of a first fuel cell element 111 A is connected to the fuel supply section 150 (not illustrated in FIG. 2 , refer to FIG. 1 ), and the fuel outlet 14 B is connected to the fuel inlet 14 A of the next fuel cell element 111 B through a connection channel 14 C. Therefore, the fuel inlet 14 A of the first fuel cell element 111 and the fuel outlet 14 B of a last fuel cell element 111 are connected to the fuel supply section 150 , and the fuel inlet 14 A of each of other fuel cell elements 111 is connected to the fuel outlet 14 B of a fuel cell element 111 previous thereto.
  • the fuel channels 40 of all fuel cell elements 111 are connected in series to one another, and the fuel F 2 supplied from the fuel supply section 150 enters the fuel inlet 14 A of the first fuel cell element 111 A, and exits from the fuel outlet 14 B of the first fuel cell element 111 A to enter the fuel inlet 14 A of the next fuel cell element 111 B, and after the fuel F 2 flows through all of the fuel cell elements 111 in the same manner, the fuel F 2 exits from the outlet 14 B of the last fuel cell element 111 to return to the fuel supply section 150 .
  • the fuel inlets 14 A and the fuel outlets 14 B, and the electrolytic solution inlets 24 A and the electrolytic solution outlets 24 B may be configured of, for example, joints made of a resin or channels formed by bonding a resin sheet having adhesion together.
  • the connection channels 14 C and 24 C may be configured of silicone tubes.
  • the connection channels 14 C and 24 C may be configured of channels formed by bonding a resin sheet having adhesion together.
  • the electrolytic solution inlets 24 A and the electrolytic solution outlets 24 B, and the fuel inlets 14 A and the fuel outlets 14 B are not necessarily formed in the external members 24 and 14 , respectively, and may be arranged in only one of the external member 24 A and the external member 14 A. In this case, an internal channel configuration allows the electrolytic solution F 1 and the fuel F 2 to be distributed to the electrolytic solution channel 30 and the fuel channel 40 , respectively.
  • a separation room is arranged in each of the connection channels 24 C and 14 C.
  • a diffused fuel methanol
  • carbon dioxide bubbles generated in the fuel electrode 10 , or the like are contained in the electrolytic solution F 1 emitted from the electrolytic solution outlet 24 B
  • the separation room 160 arranged in the connection channel 24 C removes such carbon dioxide or separates the fuel.
  • carbon dioxide bubbles generated in the fuel electrode 10 or the like are contained in the fuel F 2 emitted from the fuel outlet 14 B
  • the separation room 160 arranged in the connection channel 14 C removes carbon dioxide.
  • a methanol separation mechanism is configured of, for example, a filter, or a mechanism removing methanol by burning, reacting or evaporating methanol.
  • a mechanism removing carbon dioxide is configured of, for example, a mechanism removing carbon dioxide by a filter or reacting carbon dioxide.
  • the separation room 160 is not necessarily arranged in each of the connection channels 24 C and 14 C, and may be arranged on a top surface, a bottom surface or a side surface of each of the fuel cell elements 111 .
  • the plurality of fuel cell elements of the fuel cell stack 110 are electrically connected to one another in series or depending on specifications, in parallel.
  • deterioration of the fuel cell elements 111 occurs.
  • the fuel cell elements 111 vary slightly in characteristics without exception, so a fuel cell element 111 which is easily deteriorated and a fuel cell element 111 which is resistant to deterioration are produced.
  • the fuel cell stack 110 preferably has an electrical circuit configuration in which when the fuel cell element 111 which is not at all allowed to contribute to electric power generation due to deterioration is produced, the fuel cell stack 110 terminates electrical connection to the fuel cell element 111 , and establishes direct connection to the next fuel cell element 111 .
  • the measurement section 120 illustrated in FIG. 1 measures the operating voltage and the operating current of the fuel cell stack 110 , and includes, for example, a voltage measurement circuit 121 measuring the operating voltage of the fuel cell stack 110 and a current measurement circuit 122 measuring the operating current, and a communication line 123 for transmitting an obtained measurement result to the control section 130 .
  • the control section 130 illustrated in FIG. 1 controls an electrolyte supply parameter and a fuel supply parameter as the operating conditions of the fuel cell stack 110 based on the measurement result from the measurement section 120 , and includes, for example, a computing section 131 , a storage (memory) section 132 , a communication section 133 and a communication line 134 .
  • the electrolyte supply parameter contains, for example, the supply flow velocity of the electrolytic solution F 1 .
  • the fuel supply parameter contains, for example, the supply flow velocity and the supply amount of the fuel F 2 , and may contain a supply concentration, if necessary.
  • the control section 130 may be configured of, for example, a microcomputer.
  • the computing section 131 calculates the output of the fuel cell stack 110 from the measurement result obtained by the measurement section 120 so as to set the electrolyte supply parameter and the fuel supply parameter. More specifically, the computing section 131 calculates the averages of anode potentials, cathode potentials, output voltages and output currents sampled from various measurement results inputted into the storage section 132 at regular intervals to obtain an average anode potential, an average cathode potential, an average output voltage and an average output current, and then input them into the storage section 132 , and intercompares various average values stored in the storage section 132 to determine the electrolyte supply parameter and the fuel supply parameter.
  • the storage section 132 stores various measurement values transmitted from the measurement section 120 , various average values calculated by the computing section 131 , and the like.
  • the communication section 133 has a function of receiving the measurement result from the measurement section 120 through the communication line 123 to input the measurement result to the storage section 132 , and a function of outputting signals setting the electrolytic solution supply parameter and the fuel supply parameter to the electrolytic solution supply section 140 and the fuel supply section 150 , respectively, through the communication line 134 .
  • the electrolytic solution supply section 140 illustrated in FIG. 1 includes an electrolytic solution storage section 141 , an electrolytic solution supply adjustment section 142 and an electrolytic solution supply line 143 .
  • the electrolytic solution storage section 141 stores the electrolytic solution F 1 , and is configured of, for example, a tank or a cartridge.
  • the electrolytic solution supply adjustment section 142 adjusts the supply flow velocity of the electrolytic solution F 1 .
  • the electrolytic solution supply adjustment section 142 may be configured of any component which is allowed to be driven by a signal from the control section 130 , and is not specifically limited, but the electrolytic solution supply adjustment section 142 is preferably configured of, for example, a valve driven by a motor or a piezoelectric device or an electromagnetic pump.
  • the fuel supply section 150 illustrated in FIG. 1 includes a fuel storage section 151 , a fuel supply adjustment section 152 and a fuel supply line 153 .
  • the fuel storage section 151 stores the fuel F 2 , and is configured of, for example, a tank or a cartridge.
  • the fuel supply adjustment section 152 adjusts the supply flow velocity and the supply amount of the fuel F 2 .
  • the fuel supply adjustment section 152 may be configured of any component which is allowed to be driven by a signal from the control section 130 , and is not specifically limited, but the fuel supply adjustment section 152 is preferably configured of, for example, a valve driven by a motor or a piezoelectric device or an electromagnetic pump.
  • the fuel supply section 150 may include a concentration adjustment section (not illustrated) adjusting the supply concentration of the fuel F 2 .
  • the concentration adjustment section is allowed to be removed in the case where pure (99.9%) methanol is used as the fuel F 2 , thereby the size of the fuel supply section 150 is allowed to be further reduced.
  • the fuel cell stack system 1 is manufacturable by, for example, the following steps.
  • an alloy including platinum (Pt) and ruthenium (Ru) at a predetermined ratio as the catalyst and a dispersion solution of a polyperfluoroalkyl sulfonic acid-based resin (“Nafion (a registered trademark)” manufactured by E. I. du Pont de Nemours and Company) are mixed at a predetermined ratio to form the catalyst layer 11 of the fuel electrode 10 .
  • the catalyst layer 11 is thermal compression bonded to the diffusion layer 12 made of the above-described material.
  • the current collector 13 made of the above-described material is thermal compression bonded with a hot-melt adhesive or a resin sheet having adhesion to form the fuel electrode 10 .
  • carbon-supported platinum as the catalyst and a dispersion solution of a polyperfluoroalkyl sulfonic acid-based resin (“Nafion (a registered trademark)” manufactured by E. I. du Pont de Nemours and Company) are mixed at a predetermined ratio to form the catalyst layer 21 of the oxygen electrode 20 .
  • the catalyst layer 21 is thermal compression bonded to the diffusion layer 22 made of the above-described material.
  • the current collector 23 made of the above-described material is thermal compression bonded with a hot-melt adhesive or a resin sheet having adhesion to form the oxygen electrode 20 .
  • a resin sheet having adhesion is prepared, and a channel is formed with the resin sheet to form the electrolytic solution channel 30 and the fuel channel 40 , and the electrolytic solution channel 30 and the fuel channel 40 are thermal compression bonded to both sides of the fuel electrode 10 .
  • the external members 14 and 24 made of the above-described material are formed, and in the external member 14 , the fuel inlet 14 A and the fuel outlet 14 B are arranged, and in the external member 24 , the electrolytic solution inlet 24 A and the electrolytic solution outlet 24 B are arranged.
  • the fuel electrode 10 and the oxygen electrode 20 are arranged so as to face each other so that the electrolytic solution channel 30 is arranged between the fuel electrode 10 and the oxygen electrode 20 and the fuel channel 40 is arranged outside, and the fuel electrode 10 and the oxygen electrode 20 are contained in the external members 14 and 24 . Thereby, one fuel cell element illustrated in FIG. 2 is formed.
  • the plurality of fuel cell elements 111 are formed in the same manner, and are stacked in a vertical direction, and the electrolytic solution outlet 24 B of one fuel cell element is connected to the electrolytic solution inlet 24 A of the next fuel cell element 111 through the connection channel 24 C, and the fuel outlet 14 B of the one fuel cell element is connected to the fuel inlet 14 A of the next fuel cell element 111 through the connection channel 14 C. Moreover, the separation room 160 is connected to a midpoint of each of the connection channels 14 C and 24 C. Thereby, the fuel cell stack 110 is formed.
  • the fuel cell stack 110 is mounted in a system including the measurement section 120 , the control section 130 , the electrolytic solution supply section 140 and the fuel supply section 150 all having the above-described configurations, and the fuel inlet 14 A of the first fuel cell element 111 and the fuel outlet 14 B of the last fuel cell element 111 are connected to the fuel supply section 150 with the fuel supply line 153 configured of, for example, a silicone tube. Moreover, the electrolytic solution inlet 24 A of the first fuel cell element 111 and the electrolytic solution outlet 24 B of the last fuel cell element 111 are connected to the electrolytic solution supply section 140 with the electrolytic solution supply line 143 configured of, for example, a silicone tube.
  • the fuel cell stack system 1 illustrated in FIG. 1 is completed.
  • the fuel F 2 is supplied to the fuel electrode 10 to produce protons and electrons by a reaction.
  • the protons move to the oxygen electrode 20 through the electrolytic solution F 1 to react with electrons and oxygen, thereby to produce water.
  • Reactions occurring in the fuel electrode 10 , the oxygen electrode 20 and the whole fuel cell elements 111 are represented by Chemical Formula 2. Thereby, a part of chemical energy of methanol as the fuel is converted into electrical energy, and a current is extracted from the fuel cell stack 110 to drive the external circuit 2 .
  • Fuel electrode 10 CH 3 OH+H 2 O ⁇ CO 2 +6e ⁇ +6H 30
  • Oxygen electrode 20 (3/2)O 2 +6e ⁇ +6H + ⁇ 3H 2 O
  • the operating voltage and the operating current of the fuel cell stack 110 are measured by the measurement section 120 , and the above-described electrolytic solution supply parameter and the above-described fuel supply parameter as operating conditions of the fuel cell stack 110 are controlled by the control section 130 according to measurement results. Measurement by the measurement section 120 and parameter control by the control section 130 are frequently repeated so as to optimize the supply states of the electrolytic solution F 1 and the fuel F 2 according to variations in characteristics of the fuel cell stack 110 .
  • the electrolytic solution channels 30 and the fuel channels 40 of all of four fuel cell elements 111 are connected in series to one another.
  • the electrolytic solution F 1 supplied from the electrolytic solution supply section 140 enters the electrolytic solution inlet 24 A of the first fuel cell element 111 A, and exits from the electrolytic solution outlet 24 B of the first fuel cell element 111 A to enter the electrolytic solution inlet 24 A of the next fuel cell element 111 B, and after the electrolytic solution F 1 flows through all of the fuel cell elements 111 in the same manner, the electrolytic solution F 1 exits from the electrolytic solution outlet 24 B of the last fuel cell element 111 to return to the electrolytic solution supply section 140 .
  • the fuel F 2 supplied from the fuel supply section 150 enters the fuel inlet 14 A of the first fuel cell element 111 A, and exit from the fuel outlet 14 B of the first fuel cell element 111 A to enter the fuel inlet 14 A of the next fuel cell element 111 B, and after the fuel F 2 flows through all of the fuel cell elements 111 in the same manner, the fuel F 2 exits from the fuel outlet 14 B of the last fuel cell element 111 to return to the fuel supply section 150 .
  • the electrolytic solution channels 30 and the fuel channels 40 of all of the plurality of fuel cell elements 111 are connected in series to one another, so the number of supply auxiliaries such as pumps or valves is reduced, thereby the configuration is allowed to be simplified. Moreover, influences such as nonuniformity of the flow of the electrolytic solution F 1 or the fuel F 2 through each of the fuel cell elements 111 , a change in pressure loss and internal characteristics are reduced, so that the fuel F 2 or the electrolytic solution F 1 is allowed to be uniformly supplied to each of the fuel cell elements 111 . Therefore, the stability of electric power generation is allowed to be improved, and the fuel cell stack system 1 is suitable for a multifunctional high-performance electronic device consuming a large amount of electric power.
  • the case where the electrolytic solution channels 30 and the fuel channels 40 of all of the plurality of fuel cell elements 111 are connected in series to one another is described; however, as illustrated in FIG. 3 , the fuel channels 40 and the electrolytic solution channels 30 of some of the plurality of fuel cell elements 111 , for example, fuel cell elements 111 A, 111 B and 111 C may be connected in series to one another, and the fuel channel 40 and the electrolytic solution channel 30 of a fuel cell element 111 D may be connected in parallel with them.
  • a fuel F 2 S and an electrolytic solution F 1 S flow through the fuel cell elements 111 A, 111 B and 111 C in series, and a fuel F 2 P and an electrolytic solution F 1 P flows through the fuel cell element 111 D in parallel with the fuel F 2 S and the electrolytic solution F 1 S.
  • one of the electrolytic solution channels 30 and the fuel channels 40 of all of the plurality of fuel cell elements 11 may be connected in series to one another.
  • FIG. 4 illustrates the case where the electrolytic solution channels 30 of all of the plurality of fuel cell elements 111 are connected in series to one another
  • FIG. 5 illustrates the case where the fuel channels 40 of all of the plurality of fuel cell elements 111 are connected in series to one another.
  • the fuel channels 40 of some of the plurality of fuel cell elements 111 may be connected in series to one another, and the electrolytic solution channels 30 of all of the plurality of fuel cell elements 111 may be connected in parallel to one another.
  • the fuel F 2 S flows through the fuel cell elements 111 A, 111 B and 111 C in series
  • the fuel F 2 P flows through the fuel cell element 111 D in parallel with the fuel F 2 S.
  • the fuel channels 40 of all of the plurality of fuel cell elements 111 may be connected in parallel to one another, and the electrolytic solution channels 30 of some of the plurality of fuel cell elements 111 , for example, the fuel cell elements 111 A, 111 B and 111 C may be connected in series to one another and the electrolytic solution channel 30 of the fuel cell element 111 D may be connected in parallel to them.
  • the electrolytic solution F 1 S flows through the fuel cell elements 111 A, 111 B and 111 C in series
  • the electrolytic solution F 1 P flows through the fuel cell element 111 D in parallel with the electrolytic solution F 1 S.
  • the number of parts where the electrolytic solution channels 30 and the fuel channels 40 are connected in series is preferably increased to a maximum possible value. It is because the configuration is allowed to be further simplified, and the stability of electric power generation is allowed to be further improved.
  • FIG. 8 illustrates a schematic configuration of an electronic device including a fuel cell system according to a second embodiment.
  • the electronic device has many commonalities with the electronic device according to the above-described first embodiment, so like components will be defined as such, and not be further described in detail.
  • the electronic device is, for example, a mobile device such as a cellular phone or a PDA, or a notebook PC, and includes a fuel cell system 1 A and the external circuit (load) 2 which is driven by electrical energy generated in the fuel cell system 1 A.
  • the fuel cell system 1 A has the same configuration as that of the fuel cell stack system 1 of the first embodiment, except that, for example, instead of the fuel cell stack 110 , a fuel cell 110 A configured of one fuel cell element is included. That is, the fuel cell system 1 A includes the fuel cell 110 A, the measurement section 120 , the control section 130 , the electrolytic solution supply section 140 and the fuel supply section 150 .
  • the measurement section 120 , the control section 130 and the fuel supply section 150 are formed as in the case of the first embodiment.
  • the electrolytic solution supply section 140 includes the electrolytic solution storage section 141 , the electrolytic solution supply adjustment section 142 , the electrolytic solution supply line 143 and a separation room 144 , and allows the electrolytic solution F 1 to circulate between the fuel cell 110 A and the electrolytic solution supply section 140 .
  • the electrolytic solution storage section 141 , the electrolytic solution supply adjustment section 142 and the electrolytic solution supply line 143 are the same as those in the first embodiment.
  • the separation room 144 is configured as in the case of the separation room 160 of the first embodiment.
  • FIG. 9 illustrates a configuration of the fuel cell 110 A illustrated in FIG. 8 .
  • the fuel cell 110 A includes the electrolytic solution channel 30 , which allows the electrolytic solution F 1 to flow therethrough, between the fuel electrode 10 and the oxygen electrode 20 as in the case of the fuel cell element 111 of the first embodiment.
  • the fuel channel 40 allowing the fuel F 2 to flow therethrough is arranged on the outside of the fuel electrode 10 , that is, on a side opposite to a side where the oxygen electrode 20 is arranged.
  • the fuel electrode 10 and the oxygen electrode 20 are configured as in the case of the first embodiment.
  • FIG. 10 illustrates an outer appearance of the fuel channel 40 .
  • the fuel channel 40 is a channel structure in which a plurality of (in FIG. 10 , for example, 12 ) parallel channels 54 are arranged between a first main channel 52 connected to a main inlet 52 A for the fuel F 2 and a second main channel 53 connected to a main outlet 53 A for the fuel F 2 in a substrate 51 , and is bonded to the fuel electrode 10 .
  • the substrate 51 has, for example, a thickness of 100 ⁇ m or less, and is made of metal, glass, carbon, a resin, a porous material, silicon (Si) or a silicon (Si)-based material, or ceramic.
  • the shape of the substrate 51 may be a plate or an adhesive or non-adhesive film.
  • the substrate 51 may be configured of one plate or film, or a plurality of plates or films bonded together. In the latter case, to reliably bond the plurality of plates or films together, plates or films made of a common material are preferably bonded together, but plates or films made of different materials may be bonded together.
  • FIG. 11(A) illustrates a configuration of the fuel channel 40 when viewed from a side where the first main channel 52 , the second main channel 53 and the parallel channels 54 are arranged
  • FIG. 11(B) illustrates a sectional configuration taken along a line XIB-XIB of FIG. 11(A)
  • the first main channel 52 and the second main channel 53 are formed as grooves parallel to each other, and the widths and the heights (depths) of them are equal to each other.
  • the widths and the heights of the first main channel 52 and the second main channel 53 are not specifically limited, but the heights and the widths are preferably small, for example, 500 ⁇ m or less and 10 mm or less, respectively.
  • the first main channel 52 is connected to the fuel inlet 14 A (not illustrated in FIG. 10 , refer to FIG. 9 ) through the main inlet 52 A.
  • the second main channel 53 is connected to the fuel outlet 14 B (not illustrated in FIG. 10 , refer to FIG. 9 ) through the main outlet 54 A.
  • each of the plurality of parallel channel 54 is connected to the first main channel 52 and the second main channel 53 at a right angle, respectively, and the parallel channels 54 are formed as grooves parallel to one another.
  • the plurality of parallel channels 54 each have the same width and the same height (depth) as those of the first main channel 52 and the second main channel 53 . That is, the sectional areas of the first main channel 52 and the second main channel 53 are equal to the sectional areas of the parallel channels 54 .
  • the plurality of parallel channels 54 each have a region of which the sectional area is reduced by arranging a rib 55 at each of the inlet 54 A and the outlet 54 B. Thereby, in the fuel channel 40 , the fuel F 2 is allowed to uniformly flow through the parallel channels 54 .
  • the rib 55 has a function as a barrier to the flow of the fuel F 2 . That is, when the rib 55 is arranged, even if the substrate 51 is thinner and the sectional areas of the first main channel 52 and the second main channel 53 are equal to the sectional areas of the parallel channels 54 , the resistance of the first main channel 52 and the second main channel 53 to the flow is reduced, and on the other hand, the uniformity of the flow through the parallel channels 54 is allowed to be improved. Therefore, the thickness and the size of the fuel cell 110 A or a fuel cell stack formed by stacking the fuel cells 110 A are allowed to be remarkably reduced.
  • the rib 55 blocks a lower part of the parallel channel 54 .
  • the height H 1 of the rib 55 is dependent on the height H 0 of the parallel channel 54 , and is, for example, within a range of 1% to 99.9% of the height H 0 of the parallel channel 54 .
  • the thickness T 1 of the rib 55 depends on application, and is, for example, within a range of approximately 0.5 mm to 1 mm.
  • Such a fuel channel 40 is connected to the fuel supply section 150 (not illustrated in FIG. 9 , refer to FIG. 8 ) through the fuel inlet 14 A and the fuel outlet 14 B arranged in the external member 14 , and the fuel F 2 is supplied from the fuel supply section 150 to the fuel channel 40 .
  • FIG. 12 illustrates an outer appearance of the electrolytic solution channel 30 .
  • FIG. 13(A) illustrates a configuration of the electrolytic solution channel 30 when viewed from a side where the first main channel 52 , the second main channel 53 and the parallel channels 54 are arranged
  • FIG. 13(B) illustrates a sectional configuration taken along a line VIB-VIB of FIG. 13(A)
  • FIG. 13(C) illustrates a sectional configuration of the rib 55 in one parallel channel 54 .
  • the electrolytic solution channel 30 is a channel structure in which a plurality of (in FIG.
  • the substrate 51 is configured as in the case of the fuel channel 40 .
  • the first main channel 52 , the second main channel 53 and the parallel channels 54 allow the electrolytic solution F 1 to come into contact with both of the fuel electrode 10 and the oxygen electrode 20 (refer to FIG. 9 ), so they are configured as in the case of the fuel channel 40 , except that they are formed so as to penetrate through the substrate 51 . Moreover, as in the case of the fuel channel 40 , the sectional areas of the first main channel 52 and the second main channel 53 are equal to the sectional areas of the parallel channels 54 .
  • the plurality of parallel channels 54 each have a region of which the sectional area is reduced by arranging the rib 55 at each of the inlet 54 A and the outlet 54 B.
  • the height H 1 of the rib 55 is dependent on the height H 0 of the parallel channel 54 , and is, for example, within a range of 1% to 99.9% of the height H 0 of the parallel channel 54 .
  • the resistance of the first main channel 52 and the second main channel 53 to the flow is reduced, thereby to allow the fuel F 1 to easily flow through the first main channel 52 and the second main channel 53 , and the uniformity of the flow of the fuel F 1 through the parallel channels 54 is allowed to be improved.
  • Such an electrolytic solution channel 30 is connected to the electrolytic solution supply section 140 (not illustrated in FIG. 9 , refer to FIG. 8 ) through the electrolytic solution inlet 24 A and the electrolytic solution outlet 24 B arranged in the external member 24 , and the electrolytic solution F 1 is supplied from the electrolytic solution supply section 140 to the electrolytic solution channel 30 .
  • the fuel cell system 1 A is manufacturable by, for example, the following steps. [0119] First, as in the case of the first embodiment, the fuel electrode 10 and the oxygen electrode 20 are formed.
  • the substrate 51 made of the above-described material is prepared, and the first main channel 52 , the second main channel 53 and the parallel channels 54 illustrated in FIGS. 10 and 11 are formed in the substrate 51 , and the ribs 55 are formed at the inlets 54 A and the outlet 54 B of the parallel channels 54 so as to form the fuel channel 40 .
  • the electrolytic solution channel 30 illustrated in FIGS. 12 and 13 are formed in the same manner, and the fuel channel 40 and the electrolytic solution channel 30 are thermal compression bonded to both sides of the fuel electrode 10 .
  • the external members 14 and 24 made of the above-described material are formed, and the fuel inlet 14 A and the fuel outlet 14 B configured of, for example, joints made of a resin are arranged in the external member 14 , and the electrolytic solution inlet 24 A and the electrolytic solution outlet 24 B configured of, for example, joints made of a resin are arranged in the external member 24 .
  • the fuel electrode 10 and the oxygen electrode 20 are arranged so as to face each other so that the electrolytic solution channel 30 is arranged between the fuel electrode 10 and the oxygen electrode 20 and the fuel channel 40 is arranged outside, and the fuel electrode 10 and the oxygen electrode 20 are contained in the external members 14 and 24 . Thereby, the fuel cell 110 illustrated in FIG. 9 is completed.
  • the fuel cell 110 is mounted in a system including the measurement section 120 , the control section 130 , the electrolytic solution supply section 140 and the fuel supply section 150 all having the above-described configurations, and the fuel inlet 14 A and the fuel outlet 14 B are connected to the fuel supply section 150 through the fuel supply line 153 configured of, for example, a silicone tube, and the electrolytic solution inlet 24 A and the electrolytic solution outlet 24 B are connected to the electrolytic solution supply section 140 through the electrolytic solution supply line 143 configured of, for example, a silicone tube.
  • the fuel cell system 1 A illustrated in FIG. 8 is completed.
  • the electrolytic solution F 1 enters from the main inlet 52 A into the first main channel 52 , and then enters from the first main channel 52 into the inlets 54 A of the parallel channels 54 to flow through the parallel channels 54 , and then the electrolytic solution F 2 enters from the outlets 54 B into the second main channel 53 to exit the main outlet 53 A.
  • the region of which the sectional area is reduced by forming the rib 55 is arranged at each of the inlets 54 A and the outlets 54 B of the parallel channels 54 , so the rib 55 becomes a barrier to the flow of the fuel F 2 or the electrolytic solution F 1 , and the resistance of the first main channel 52 and the second main channel 53 to the flow is reduced, thereby to allow the fuel F 2 or the electrolytic solution F 2 to easily flow through the first main channel 52 and the second main channel 53 , and the uniformity of the flow of the fuel F 2 or the electrolytic solution F 1 through the parallel channels 54 is improved.
  • the thickness of a substrate 51 is 100 ⁇ m or less which is extremely thin, and even if the sectional areas of the first main channel 52 and the second main channel 54 are equal to the sectional areas of the parallel channels 54 , the resistance of the first main channel 52 and the second main channel 53 to the flow is reduced, and on the other hand, the uniformity of the flow through the parallel channels 54 is improved.
  • the region of which the sectional area is reduced by the rib 55 is arranged at each of the inlets 54 A and the outlets 54 B of two or more parallel channels 54 , so the fuel F 2 or the electrolytic solution F 1 is allowed to uniformly flow through the parallel channels 54 . Therefore, the electric power generation characteristics of the fuel cell 110 A are allowed to be improved, and the fuel cell system 1 A is suitable for a multifunctional high-performance electronic device consuming a large amount of electric power.
  • FIG. 14 illustrates a configuration of a fuel cell 110 B of a fuel cell system 1 A according to a third embodiment.
  • the fuel cell system 1 A has the same configuration as that of the above-described second embodiment, except that in the fuel cell 110 B, a functional layer 51 and a functional layer 52 are arranged on the fuel electrode 10 and the oxygen electrode 20 , respectively. Therefore, like components will be described using like numerals.
  • the catalyst layers 11 and 21 , the diffusion layers 12 and 22 , the current collectors 13 and 23 and the external members 14 and 24 of the fuel electrode 10 and the oxygen electrode 20 are configured as in the case of the first embodiment.
  • the functional layer (a contact inhibition layer) 51 inhibiting direct contact between the catalyst layer 11 and the electrolytic solution F 1 is arranged on the catalyst layer 11 of the fuel electrode 10 .
  • the functional layer (contact inhibition layer) 52 inhibiting direct contact between the catalyst layer 21 and the electrolytic solution F 1 is arranged on the catalyst layer 21 of the oxygen electrode 20 .
  • the functional layer 51 arranged on the fuel electrode 10 is an anti-deterioration layer preventing deterioration such as a crack or a hole of the fuel electrode 10 caused by direct contact between the catalyst layer 11 and the electrolytic solution F 1 while maintaining an ion path between the electrolytic solution F 1 and the catalyst layer 11 .
  • the functional layer 51 also has a function of reducing fuel crossover (a crossover inhibition layer) and a function of preventing carbon dioxide (CO 2 ) as bubbles generated by a reaction in the fuel electrode 10 from being released into the electrolytic solution F 1 (a bubble release direction control layer). The generated carbon dioxide as bubbles is released into both of the electrolytic solution F 1 in the electrolytic solution channel 30 and the fuel F 2 in the fuel channel 40 .
  • Carbon dioxide released into the fuel F 2 is not an issue, but carbon dioxide released into the electrolytic solution F 1 may cause a fatal issue. It is because a proton path is blocked by release of carbon dioxide bubbles to cause a change in proton conductivity and instability in characteristics in an area where bubbles are present.
  • the functional layer 51 is arranged, the direction where carbon dioxide bubbles are released is controllable, thereby to allow carbon dioxide released into the electrolytic solution F 1 to be remarkably reduced.
  • the functional layer 52 arranged in the oxygen electrode 20 is an anti-deterioration layer preventing deterioration such as a crack or a hole of the oxygen electrode 20 caused by direct contact between the catalyst layer 21 and the electrolytic solution F 1 while maintaining an ion path between the electrolytic solution F 1 and the catalyst layer 21 and preventing leakage of the electrolytic solution F 1 .
  • the functional layer 52 also has a function of preventing overvoltage generated in the oxygen electrode 20 due to fuel crossover (an overvoltage prevention layer) and a function of preventing flooding of the oxygen electrode 20 (a flooding prevention layer).
  • the oxygen electrode 20 is consistently in contact with the electrolytic solution F 1 , and is in a state in which flooding consistently occurs irrespective of whether electric power is generated or not, but when the functional layer 52 is arranged, the flooding state of the oxygen electrode 20 is allowed to be relieved.
  • the functional layers 51 and 52 are made of, for example, a porous material. An ion path between the electrolytic solution F 1 and the catalyst layers 11 and 21 is allowed to be secured by pores contained in the porous material.
  • a porous material specifically metal, carbon, a resin such as polyimide or ceramic is cited, and a blend layer made of a plurality of materials selected from them may be used.
  • the resin may be a water-repellent resin or a hydrophilic resin.
  • the thicknesses of the functional layers 51 and 52 are, for example, approximately 10 ⁇ m to 15 ⁇ m, and are preferably as thin as possible.
  • the pores of the functional layers 51 and 52 preferably have, for example, a diameter ranging from nanometers to micrometers, but they are not specifically limited. However, the diameters of the pores in the functional layers 51 and 52 are preferably smaller than the diameters of pores contained in the fuel electrode 10 or the oxygen electrode 20 . It is because it is necessary that carbon dioxide generated as bubbles selectively passes through the fuel electrode 10 to be released toward the fuel F 2 . Moreover, needless to say, a porous material with a thin pore diameter has a higher function of preventing methanol crossover than a porous material with a large pore diameter.
  • the functional layers 51 and 52 may be made of an ion conductor such as a proton conductor.
  • the proton conductor include a polyperfluoroalkyl sulfonic acid-based resin (“Nafion (a registered trademark)” manufactured by E. I. du Pont de Nemours and Company), polystyrene sulfonate, a fullerene-based conductor, a solid acid and other resin having proton conductivity.
  • the electrolytic solution channel 30 and the fuel channel 40 are configured as in the case of the first embodiment.
  • the electrolytic solution channel 30 is connected to the electrolytic solution supply section 140 (not illustrated in FIG. 14 , refer to FIG. 8 ) through the electrolytic solution inlet 24 A and the electrolytic solution outlet 24 B arranged in the external member 24 , and the electrolytic solution F 1 is supplied from the electrolytic solution supply section 140 to the electrolytic solution channel 30 .
  • the fuel channel 40 is connected to the fuel supply section 150 (not illustrated in FIG. 14 , refer to FIG. 8 ) through the fuel inlet 14 A and the fuel outlet 14 B arranged in the external member 14 , and the fuel F 2 is supplied from the fuel supply section 150 to the fuel channel 40 .
  • the fuel cell system 1 A is manufacturable by, for example, the following steps.
  • the catalyst layer 11 of the fuel electrode 10 is formed.
  • the catalyst layer 11 is thermal compression bonded to the diffusion layer 12 made of the above-described material.
  • the functional layer 51 made of the above-described material is formed on a surface where the diffusion layer 12 is not thermal compression bonded of the catalyst layer 11 .
  • a bar-coating method is preferable. It is because the functional layer 51 is applicable with a uniform thickness.
  • the method of forming the functional layer 51 is not limited to the bar coating method, and any other coating method such as a gravure coating method, a roll coating method, a spin coating method, a dip coating method, a doctor bar coating method, a wire bar coating method, a blade coating method, a curtain coating method, a spray coating method may be used.
  • another member may coated with a coating liquid including the material of the functional layer 51 , and the coating liquid may be dried to form a porous film, and then the porous film may be transferred to the catalyst layer 11 .
  • the functional layer 51 made of the above-described material may be thermal compression bonded to the catalyst layer 11 .
  • the current collector 13 made of the above-described material is thermal compression bonded with a hot-melt adhesive or a resin sheet having adhesion to form the fuel electrode 10 .
  • the catalyst layer 21 of the oxygen electrode 20 is formed.
  • the catalyst layer 21 is thermal compression bonded to the diffusion layer 22 made of the above-described material.
  • the functional layer 52 made of the above-described material is formed on a surface where the diffusion layer 22 is heat compression bonded of the catalyst layer 21 .
  • a method of forming the functional layer 52 is the same as the above-described method of forming the functional layer 51 .
  • the current collector 23 made of the above-described material is thermal compression bonded with a hot-melt adhesive or a resin sheet having adhesion to form the oxygen electrode 20 .
  • a resin sheet having adhesion is prepared, and a channel is formed with the resin sheet to form the electrolytic solution channel 30 and the fuel channel 40 , and the electrolytic solution channel 30 and the fuel channel 40 are thermal compression bonded to both sides of the fuel electrode 30 .
  • the external members 14 and 24 made of the above-described material are formed, and the fuel inlet 14 A and the fuel outlet 14 B, and the electrolytic solution inlet 24 A and the electrolytic solution outlet 24 B are arranged in the external member 14 and the external member 24 , respectively.
  • the fuel electrode 10 and the oxygen electrode 20 are arranged so as to face each other so that the electrolytic solution channel 30 is arranged between the fuel electrode 10 and the oxygen electrode 20 and the fuel channel 40 is arranged outside, and the fuel electrode 10 and the oxygen electrode 20 are contained in the external members 14 and 24 . Thereby, the fuel cell 110 B illustrated in FIG. 14 is completed.
  • the fuel cell 110 B is mounted in a system including the measurement section 120 , the control section 130 , the electrolytic solution supply section 140 and the fuel supply section 150 all having the above-described configurations, and the fuel inlet 14 A and the fuel outlet 14 B are connected to the fuel supply section 150 through the fuel supply line 153 made of, for example, a silicone tube, and the electrolytic solution inlet 24 A and the electrolytic solution outlet 24 B are connected to the electrolytic solution supply section 140 through the electrolytic solution supply line 143 made of, for example, a silicone tube.
  • the fuel cell system 1 A illustrated in FIG. 8 is completed.
  • the fuel electrode 10 is arranged between the electrolytic solution channel 30 and the fuel channel 40 , so almost all of the fuel reacts when flowing through the fuel electrode 10 . Even if the fuel F 2 passes through the fuel electrode 10 without reaction, fuel crossover is remarkably prevented by the functional layer 51 arranged on the catalyst layer 11 , and a possibility that the fuel F 2 reaches the oxygen electrode 20 is extremely low. Therefore, a high-concentration fuel is applicable, and high energy density characteristics as an intrinsic advantage of the fuel cell are utilized.
  • carbon dioxide generated in the fuel electrode 10 is prevented from being released into the electrolytic solution F 2 by the functional layer 51 arranged on the catalyst layer 11 , and the carbon dioxide is released into the fuel F 2 to flow with the fuel F 2 , thereby to be removed. Therefore, conductivity is prevented from being lost due to carbon dioxide bubbles mixed into the electrolytic solution F 1 . In addition, water generated in the oxygen electrode 20 flows with the electrolytic solution F 1 to be removed.
  • the functional layers 51 and 52 preventing direct contact between the catalyst layers 11 and 21 and the electrolytic solution F 2 are arranged on the catalyst layers 11 and 21 , so deterioration such as a crack or a hole of the fuel electrode 10 or the oxygen electrode 20 is preventable. Therefore, a decline in characteristics of the fuel cell 110 is prevented, and long-time electric power generation is allowed, and the embodiment is suitable for a multifunctional high-performance electronic device consuming a large amount of electric power.
  • the functional layers 51 and 52 are arranged in the fuel electrode 10 and the oxygen electrode 20 , respectively is described; however, for example, as illustrated in FIG. 15 , the functional layer 51 may be arranged on the catalyst layer 11 of the fuel electrode 10 , and the functional layer 52 of the oxygen electrode 20 may be removed. Moreover, as illustrated in FIG. 16 , the functional layer 52 may be arranged on the catalyst layer 21 of the oxygen electrode 20 , and the functional layer 41 of the fuel electrode 10 may be removed.
  • FIG. 17 illustrates a configuration of a fuel cell 110 B according to a fourth embodiment.
  • a gas-liquid separation film 60 is arranged between the fuel channel 40 and the fuel electrode 10 , and the fuel cell 110 B is configured as in the case of the above-described third embodiment, except for this. Therefore, like components will be described using like numerals.
  • the gas-liquid separation film 60 may be configured of, for example, a film not allowing alcohol in a liquid form to pass therethrough such as polytetrafluoroethylene (PTFE), polyvinylidene fluoride (PVDF) or polypropylene (PP).
  • PTFE polytetrafluoroethylene
  • PVDF polyvinylidene fluoride
  • PP polypropylene
  • the fuel cell 110 B and the fuel cell system 1 A using the fuel cell 110 B are manufacturable as in the case of the above-described embodiments, except that the gas-liquid separation film 60 is arranged between the fuel channel 40 and the fuel electrode 10 .
  • a current is extracted from the fuel cell 110 B to drive the external circuit 2 .
  • the gas-liquid separation film 60 is arranged between the fuel channel 40 and the fuel electrode 10 , when pure methanol as the fuel flows through the fuel channel 40 in a liquid form, pure methanol volatilizes spontaneously, and passes through the gas-liquid separation film 60 in the form of a gas G from a surface in contact with the gas-liquid separation film 60 to be supplied to the fuel electrode 10 . Therefore, the fuel is efficiently supplied to the fuel electrode 10 , and a reaction stably occurs. Moreover, the fuel is supplied to the fuel electrode 10 in a gas form, so electrode reaction activity is improved, and crossover is less prone to occur, and high performance is obtained in an electronic device including a high-load external circuit 2 .
  • the gas-liquid separation film 60 is arranged between the fuel channel 40 and the fuel electrode 10 , pure (99.9%) methanol is applicable as the fuel F 2 , and high energy density characteristics as an advantage of the fuel cell is allowed to be further utilized. Moreover, reaction stability or electrode reaction activity is allowed to be improved, and crossover is preventable. Therefore, also in an electronic device having the high-load external circuit 2 , high performance is obtainable. Further, in the fuel supply section 150 , a concentration adjustment section adjusting the supply concentration of the fuel F 2 is allowed to be removed, so the size of the fuel supply section 150 is allowed to be further reduced.
  • FIGS. 18 and 19 illustrate a configuration of a channel structure according to a fifth embodiment.
  • a channel structure 200 is used as, for example, a micro TAS, and includes a channel 220 for fluid formed in a base 210 and a fluid connector 230 connected to the channel 220 .
  • the base 210 is formed by cutting a thin plate made of glass, silicon (Si) or the like or bonding the thin plates together or bonding flexible films such as plastic films together. More specifically, as illustrated in FIG. 20 , the base 210 is formed by cutting a thin plate 210 A made of metal, plastic or the like to form the channel 220 , and bonding another thin plate or flexible film 210 B to the thin plate 210 A, or as illustrated in FIG. 21 , the base 210 is formed by bonding a thin plate or flexible film 210 C in which an incision corresponding to the shape of the channel 220 is arranged to another thin plates or flexible films 210 B and 210 D. Therefore, the sectional shape of the channel 220 is rectangular.
  • the planar shape of the channel 220 is not specifically limited.
  • the end 221 on the inlet side is not necessarily arranged only at one point, and the ends 221 on the inlet side may be arranged at two or more points, and different fluids may be introduced into the channel 220 from the ends 221 , respectively.
  • the fluid connector 230 introduces and guides the fluid into the channel 220 from an external system (not illustrated), and has a different sectional shape from the sectional shape of the channel 220 .
  • the sectional shape of the channel 220 is rectangular as described above, but the fluid connector 230 is, for example, a cylindrical tube made of polyolefin.
  • the fluid connector 230 is connected to a main surface of the base 210 in a direction parallel to the channel 220 . Thereby, in the channel structure 200 , a space for connection of the fluid connector 230 is allowed to be reduced.
  • the ends 221 of the channel 220 are formed in projections 211 projected from a side surface of the base 210 in a direction parallel to the main surface of the base 210 , and the fluid connector 230 is connected to the projections 211 , and a heat-shrinkable tube 240 is arranged on a connection part between the projection 211 and the fluid connector 230 .
  • the heat-shrinkable tube 240 allows connection between the channel 220 and the fluid connector 230 with different sectional shapes, and is made of, for example, polyolefin.
  • the heat-shrinkable tube 240 when the heat-shrinkable tube 240 is arranged, even if the base 210 is thinner than the tube diameter (outside diameter) of the fluid connector 230 , the fluid connector 230 is connectable in a direction parallel to the main surface of the base 210 , and the base 210 is allowed to be extremely thin.
  • the projections 211 may be projected in parallel with the main surface of the base 210 , and are not necessarily projected in a direction perpendicular to the side surface of the base 210 .
  • the channel structure 200 is manufacturable by, for example, the following steps.
  • the thin plate 210 A is cut to form the channel 220 , and the channel 220 is bonded to another thin plate 210 B, or as illustrated in FIG. 21 , the thin plate or flexible film 210 B in which an incision corresponding to the shape of the channel 220 is arranged is bonded to another thin plates or flexible films 210 B and 210 D, thereby the base 210 including the channel 220 inside thereof is formed.
  • the projections 211 projected from the side surface of the base 210 in a direction parallel to the main surface of the base 210 are arranged, and the ends 221 of the channel 220 are formed in the projections 211 .
  • the heat-shrinkable tube 240 made of the above-described material is prepared, and the projection 211 is put into an end of the heat-shrinkable tube 240 .
  • a part put on the projection 211 of the heat-shrinkable tube 240 is adhered to the projection 211 .
  • an adhesive may be used, or a surface of the projection 211 and the inside of the heat-shrinkable tube 240 may be made of a material having thermal adhesion.
  • the fluid connector 230 made of the above-described material is prepared, and the fluid connector 230 is put into the other end of the heat-shrinkable tube 240 , and a part put on the fluid connector 230 of the heat-shrinkable tube 240 is adhered to the fluid connector 230 .
  • an adhesive may be used, or a surface of the fluid connector 230 and the inside of the heat-shrinkable tube 240 may be made of a material having thermal adhesion.
  • the fluid connector 230 may be put into the ends 221 of the channel 220 in the projection 211 .
  • the channel structure 200 illustrated in FIGS. 18 and 19 is completed.
  • the fluid is introduced into the channel 220 from the external system (not illustrated) through the fluid connector 230 and the end 221 on the inlet side, and the mixture, reaction, separation, detection or the like is performed on the fluid in the channel 220 , and then the fluid is emitted from the end 221 on the outlet side through the fluid connector 230 .
  • the fluid connector 230 is connected to the channel 220 in a direction parallel to the main surface of the base 210 , so a space for connection of the fluid connector 230 is allowed to be reduced. Therefore, the bases 210 to which the fluid connector 230 is connected are allowed to be stacked in parallel, and integration is allowed to be improved.
  • FIG. 22 illustrates the end 221 of the channel 220 according to a modification example.
  • the fluid connector 230 is connected to the channel 220 with an auxiliary component 250 in between, and the heat-shrinkable tube 240 is arranged between auxiliary component 250 and the fluid connector 230 .
  • the fluid connector 230 is connectable to the channel 220 in a direction parallel to the main surface of the base 210 , and a space for connection of the fluid connector 230 is allowed to be reduced, and integration is allowed to be improved.
  • auxiliary component 250 a curved channel 251 curved at 90° from the end 221 of the channel 220 is formed, and as illustrated in FIG. 23 , the auxiliary component 250 is formed by bonding three films 252 A, 252 B and 252 C made of plastic together.
  • a connection hole 252 A 1 connected to the end 221 of the channel 220 is arranged.
  • a cutout part 252 B with a shape corresponding to the curved channel 251 is arranged.
  • a thermosetting adhesive (not illustrated) is arranged on both sides of the film 252 B, thereby the films 252 A to 252 C are allowed to be bonded together by stacking them and applying heat to them.
  • an adhesive may be arranged on a back surface of the film 252 A so as to be used for adhesion to the base 210 which is desired to be connected.
  • FIG. 24 illustrates an example in which the channel structure 200 is applied to a fuel channel of a fuel cell.
  • the fuel cell is a so-called polymer electrolyte fuel cell (PEFC), and includes an electrolyte film 263 between a fuel electrode (anode) 261 and an oxygen electrode (cathode) 262 .
  • the channel structure 200 according to the above-described embodiment is arranged on the outside of the fuel electrode 261 , and methanol as a fuel is supplied to the fuel electrode 261 through the channel 220 of the channel structure 200 .
  • the fuel electrode 261 is arranged instead of the thin plate or flexible film 210 B illustrated in FIGS. 20 and 21 , and the fuel in the channel 220 is allowed to come into contact with the fuel electrode 261 .
  • An external member 264 configured of a titanium (Ti) plate or the like is arranged on the outside of the oxygen electrode 262 .
  • the fuel electrode 261 and the oxygen electrode 262 are formed by forming a catalyst layer including platinum (Pt), ruthenium (Ru) or the like on a surface of a carbon cloth or the like, and then arranging a current collector configured of a titanium (Ti) mesh on a back surface of the carbon cloth or the like.
  • the electrolyte film 263 is configured of, for example, a polyperfluoroalkyl sulfonic acid-based resin (“Nafion (a registered trademark)” manufactured by E. I. du Pont de Nemours and Company) or another resin film having proton conductivity.
  • the fuel electrode 261 , the oxygen electrode 262 and the electrolyte film 263 are fixed by a gasket (not illustrated).
  • the fuel cell is manufacturable by, for example, the following steps.
  • the channel structure 200 of the above-described embodiment is arranged on the outside of the fuel electrode 261 , and the external member 263 made of the above-described material is arranged on the outside of the oxygen electrode 262 .
  • the fuel cell illustrated in FIG. 24 is completed.
  • battery reactions by Chemical Formula 2 occur.
  • methanol as the fuel is introduced into the channel 220 from an external fuel tank (not illustrated) through the fluid connector 230 and the end 221 on the inlet side to come into contact with the catalyst layer of the fuel electrode 261 in the channel 220 , thereby a battery reaction by a first formula in Chemical Formula 2 occurs, and then methanol is emitted from the end 221 on the outlet side through the fluid connector 230 .
  • the channel structure 200 according to the above-described embodiment is arranged as a fuel supply path, so a space for connection of the fluid connector 230 is allowed to be reduced, and the thickness of the fuel channel is allowed to be reduced. Therefore, the fuel cells with a smaller thickness are allowed to be stacked in parallel, and integration is allowed to be improved.
  • FIG. 25 illustrates a configuration example of another fuel cell to which the channel structure 200 of the above-described fifth embodiment is applied.
  • the channel structure 200 of the above-described embodiment is arranged, and an electrolytic solution (for example, a sulfuric acid) as a liquid electrolyte is supplied between the fuel electrode 261 and the oxygen electrode 262 .
  • an electrolytic solution for example, a sulfuric acid
  • the fuel cell of the application example is configured as in the case of the above-descried Application Example 1.
  • the fluid connector 230 of the channel structure 200 as a fuel channel and the fluid connector 230 of the channel structure 200 as an electrolytic solution channel are not necessarily connected to different positions as illustrated in FIG. 25 , and may be stacked so as to be connected to a common position.
  • the fuel cell is manufacturable as in the case of the above-described Application Example 1, except that instead of the electrolyte film 263 , the channel structure 200 of the above-described embodiment is arranged.
  • the fuel is supplied to the fuel electrode 261 through the channel 220 of the channel structure 200 as in the case of the above-described application example.
  • the electrolytic solution is introduced into the channel 220 from an external electrolytic solution tank (not illustrated) through the fluid connector 230 and the end 221 on the inlet side, and is emitted with carbon dioxide or the like generated in the reaction from the end 221 on the outlet side through the fluid connector 230 .
  • the fuel having passed through the fuel electrode 261 is also removed with the electrolytic solution before reaching the oxygen electrode 262 , thereby crossover is prevented.
  • the channel structure 200 according to the above-described embodiment is also arranged as an electrolytic solution supply path, so a space for connection of the fluid connector 230 is allowed to be reduced, and a gap between the fuel electrode 261 and the oxygen electrode 262 is allowed to be reduced. Therefore, the fuel cells with a smaller thickness are allowed to be stacked in parallel, and integration is allowed to be improved.
  • Example 1 the fuel cell stack 110 configured of two fuel cell elements 111 A and 111 B as illustrated in FIG. 2 was formed, and its characteristics were evaluated. Therefore, referring to FIGS. 1 and 2 , like components will be described using like numerals.
  • the fuel cell stack 110 having the same configuration illustrated in FIG. 2 was formed.
  • an alloy including platinum (Pt) and ruthenium (Ru) at a predetermined ratio as a catalyst and a dispersion solution of a polyperfluoroalkyl sulfonic acid-based resin (“Nafion (a registered trademark)” manufactured by E. I. du Pont de Nemours and Company) were mixed at a predetermined ratio to form the catalyst layer 11 of the fuel electrode 10 .
  • the catalyst layer 11 was thermal compression bonded to the diffusion layer 12 made of the above-described material (HT-2500 manufactured by E-TEK Inc.) for 10 minutes under the conditions where the temperature was 150° C. and the pressure was 249 kPa.
  • the current collector 13 made of the above-described material was thermal compression bonded with a hot-melt adhesive or a resin sheet having adhesion to form the fuel electrode 10 .
  • carbon-supported platinum (Pt) as a catalyst and a dispersion solution of a polyperfluoroalkyl sulfonic acid-based resin (“Nafion (a registered trademark)” manufactured by E. I. du Pont de Nemours and Company) were mixed at a predetermined rate to form the catalyst layer 21 of the oxygen electrode 20 .
  • the catalyst layer 21 was thermal compression bonded to the diffusion layer 22 made of the above-described material (HT-2500 manufactured by E-TEK Inc.) as in the case of the catalyst layer 11 of the fuel electrode 10 .
  • the current collector 23 made of the above-described material was thermal compression bonded as in the case of the current collector 13 of the fuel electrode 10 to form the oxygen electrode 20 .
  • the resin sheet having adhesion was prepared, and a channel was formed with the resin sheet to form the electrolytic solution channel 30 and the fuel channel 40 , and the electrolytic solution channel 30 and the fuel channel 40 were thermal compression bonded to both sides of the fuel electrode 10 .
  • the external members 14 and 24 made of the above-described material were formed, and the fuel inlet 14 A and the fuel outlet 14 B configured of, for example, joints made of a resin were arranged in the external member 14 , and the electrolytic solution inlet 24 A and the electrolytic solution outlet 24 B configured of, for example, joints made of a resin were arranged in the external member 24 .
  • the fuel electrode 10 and the oxygen electrode 20 were arranged so as to face each other so that the electrolytic solution channel 30 was arranged between the fuel electrode 10 and the oxygen electrode 20 and the fuel channel 40 was arranged outside, and the fuel electrode 10 and the oxygen electrode 20 were contained in the external members 14 and 24 .
  • two fuel cell elements 111 A and 111 B were formed, and stacked in a vertical direction, and the electrolytic solution channels 30 and the fuel channels 40 of two fuel cell elements 111 A and 111 B were connected in series to each other. That is, the electrolytic solution outlet 24 B of the fuel cell element 111 A was connected to the electrolytic solution inlet 24 A of the fuel cell element 111 B through the connection channel 24 C configured of a silicone tube, and the fuel outlet 14 B of the fuel cell element 111 A was connected to the fuel inlet 14 A of the fuel cell element 111 B through the connection channel 14 C configured of a silicone tube. Moreover, the separation room 160 was connected to a midpoint of each of the connection channels 14 C and 24 C. Thereby, the fuel cell stack 110 illustrated in FIG. 2 was completed.
  • the fuel cell stack 110 was mounted in a system including the measurement section 120 , the control section 130 , the electrolytic solution supply section 140 and the fuel supply section 150 all having the above-described configurations so as to form the fuel cell stack system 1 illustrated in FIG. 1 .
  • the electrolytic solution supply adjustment section 142 and the fuel supply adjustment section 152 were configured of diaphragm type quantitative pumps (manufactured by KNF Neuberger GmbH).
  • the fuel inlet 14 A of the fuel cell element 111 A and the fuel outlet 14 B of the fuel cell element 111 B were connected to the pump of the fuel supply adjustment section 152 through the fuel supply line 153 configured of a silicone tube
  • the electrolytic solution inlet 24 A of the fuel cell element 111 A and the electrolytic solution outlet 24 B of the fuel cell element 111 B were connected to the pump of the electrolytic solution supply adjustment section 142 through the electrolytic solution supply line 143 configured of a silicone tube
  • the electrolytic solution F 1 and the fuel F 2 were supplied to the electrolytic solution channel 30 and the fuel channel 40 at an arbitrary flow velocity, respectively.
  • As the electrolytic solution F 1 1M sulfuric acid was used, and the flow velocity was 1.0 ml/min.
  • As the fuel F 2 a mixed liquid of 5M methanol and 1M sulfuric acid was used, and the flow velocity was 0.5 ml/min.
  • the obtained fuel cell stack system 1 was connected to an electrochemical measurement system (Multistat 1480 manufactured by Solartoron Co., Ltd), and the characteristics of the fuel cell system 1 were evaluated.
  • the characteristics of each of the fuel cell elements 111 A and 111 B and the fuel cell stack 110 when generating electric power at an open circuit voltage (OCV) in an initial stage of measurement and a constant current of 1 A were examined. The results are illustrated in FIGS. 26 and 27 .
  • FIG. 26 illustrates the OCV in the initial state of measurement.
  • FIG. 26 illustrates a state in which the OCV was maintained for approximately 180 seconds, and the OCD showed a high value, and increased.
  • the value of the OCV was 1.3 V or over, so the OCV of each fuel cell element was 0.65 V or over, and showed a much higher value than the OCV (approximately 0.4 V to 0.5 V) of a typical DMFC. It was considered that fuel crossover was prevented by using the electrolytic solution F 1 .
  • the value of the OCV of the fuel cell stack 110 was approximately twice as high as the value of the OCV of each of the fuel cell elements 111 A and 111 B, so it appeared that there was no harm in connecting the electrolytic solution channels 30 and the fuel channels 40 in series to one another.
  • the fuel cell 110 A was formed.
  • an alloy including platinum (Pt) and ruthenium (Ru) at a predetermined ratio as a catalyst and a dispersion solution of a polyperfluoroalkyl sulfonic acid-based resin (“Nafion (a registered trademark)” manufactured by E. I. du Pont de Nemours and Company) were mixed at a predetermined ratio to form the catalyst layer 11 of the fuel electrode 10 .
  • the catalyst layer 11 was thermal compression bonded to the diffusion layer 12 made of the above-described material (HT-2500 manufactured by E-TEK Inc.) for 10 minutes under the conditions where the temperature was 150° C. and the pressure was 249 kPa.
  • the current collector 13 made of the above-described material was thermal compression bonded with a hot-melt adhesive or a resin sheet having adhesion to form the fuel electrode 10 .
  • carbon-supported platinum (Pt) as a catalyst and a dispersion solution of a polyperfluoroalkyl sulfonic acid-based resin (“Nafion (a registered trademark)” manufactured by E. I. du Pont de Nemours and Company) were mixed at a predetermined rate to form the catalyst layer 21 of the oxygen electrode 20 .
  • the catalyst layer 21 was thermal compression bonded to the diffusion layer 22 made of the above-described material (HT-2500 manufactured by E-TEK Inc.) as in the case of the catalyst layer 11 of the fuel electrode 10 .
  • the current collector 23 of the above-described material was thermal compression bonded as in the case of the current collector 13 of the fuel electrode 10 to form the oxygen electrode 20 .
  • the substrate 51 configured of the resin sheet having adhesion was prepared, and the first main channel 52 , the second main channel 53 and the parallel channels 54 illustrated in FIGS. 10 and 11 were formed in the substrate 51 , and the ribs 55 were formed in the inlets 54 A and the outlets 54 B of the parallel channels 54 to form the fuel channel 40 .
  • the electrolytic solution channel 30 illustrated in FIGS. 12 and 13 was formed in the same manner, and the fuel channel 40 and the electrolytic solution channel 30 were thermal compression bonded to both sides of the fuel electrode 10 .
  • the external members 14 and 24 made of the above-described material were formed, and the fuel inlet 14 A and the fuel outlet 14 B configured of, for example, joints made of a resin were arranged in the external member 14 , and the electrolytic solution inlet 24 A and the electrolytic solution outlet 24 B configured of, for example, joints made of a resin were arranged in the external member 24 .
  • the fuel electrode 10 and the oxygen electrode 20 were arranged so as to face each other so that the electrolytic solution channel 30 was arranged between the fuel electrode 10 and the oxygen electrode 20 and the fuel channel 40 was arranged outside, and the fuel electrode 10 and the oxygen electrode 20 were contained in the external members 14 and 24 .
  • the fuel cell 110 A was mounted in a system including the measurement section 120 , the control section 130 , the electrolytic solution supply section 140 and the fuel supply section 150 all having the above-described configurations so as to form the fuel cell system 1 A illustrated in FIG. 8 .
  • the electrolytic solution supply adjustment section 142 and the fuel supply adjustment section 152 were configured of diaphragm type quantitative pumps (manufactured by KNF Neuberger GmbH), and the pumps were directly connected to the electrolytic solution inlet 24 B and the fuel inlet 14 A through the electrolytic solution supply line 143 and the fuel supply line 153 configured of silicone tubes, respectively, and the electrolytic solution F 1 and the fuel F 2 were supplied to the electrolytic solution channel 30 and the fuel channel 40 at an arbitrary flow velocity, respectively.
  • electrolytic solution F 1 1M sulfuric acid was used, and the flow velocity was 1.0 ml/min.
  • fuel F 2 a mixed liquid of 5M methanol and 1M sulfuric acid was used, and the flow velocity was 0.5 ml/min.
  • the flow velocity ratio distributions in 18 parallel channels 54 in the obtained fuel cell system 1 A were determined. The results are illustrated in FIG. 28 .
  • velocity distributions in the parallel channels 54 when changing the height H 1 of the rib 55 based on a flow velocity ratio 1 were illustrated as a ratio.
  • channel numbers 1 to 18 are assigned to parallel channels 54 in order from a side near the main inlet 52 A.
  • the fuel cell systems 1 A were formed as in the case of the above-described Example 2, except that the number N of the parallel channels 54 was changed to 1, 6, 12 and 18.
  • Electric power generation characteristics of the obtained fuel cell systems 1 A were examined.
  • the height H 0 and the width of the parallel channel 54 was 175 ⁇ m and 2 mm, respectively, and the height H 1 of the rib 55 was slightly less than 40% of the height H 0 of the parallel channel 54 .
  • the measurement voltage was 0.3 V, and the data 180 seconds after the start of electric power generation at a constant voltage of 0.3 V was taken. The obtained results are illustrated in FIG. 29 .
  • the fuel cell 110 B having the same configuration of that in FIG. 15 was formed.
  • an alloy including platinum (Pt) and ruthenium (Ru) at a predetermined ratio as a catalyst and a dispersion solution of a polyperfluoroalkyl sulfonic acid-based resin (“Nafion (a registered trademark)” manufactured by E. I. du Pont de Nemours and Company) were mixed at a predetermined ratio to form the catalyst layer 11 of the fuel electrode 10 .
  • the catalyst layer 11 was thermal compression bonded to the diffusion layer 12 made of the above-described material (HT-2500 manufactured by E-TEK Inc.) for 10 minutes under the conditions where the temperature was 150° C. and the pressure was 249 kPa.
  • the functional layer 51 a fine porous film made of polyimide with a thickness of approximately 10 ⁇ m to 15 ⁇ m was prepared, and the functional layer 51 was thermal compression bonded to the catalyst layer 11 for 5 minutes under the conditions where the temperature was 150° C. and the pressure was 249 kPa. Further, the current collector 13 made of the above-described material was thermal compression bonded with a hot-melt adhesive or a resin sheet having adhesion to form the fuel electrode 10 .
  • carbon-supported platinum (Pt) as a catalyst and a dispersion solution of a polyperfluoroalkyl sulfonic acid-based resin (“Nafion (a registered trademark)” manufactured by E. I. du Pont de Nemours and Company) were mixed at a predetermined rate to form the catalyst layer 21 of the oxygen electrode 20 .
  • the catalyst layer 21 was thermal compression bonded to the diffusion layer 22 made of the above-described material (HT-2500 manufactured by E-TEK Inc.) as in the case of the catalyst layer 11 of the fuel electrode 10 .
  • the current collector 23 of the above-described material was thermal compression bonded as in the case of the current collector 13 of the fuel electrode 10 to form the oxygen electrode 20 .
  • a resin sheet having adhesion was prepared, and the channel was formed with the resin sheet to form the electrolytic solution channel 30 and the fuel channel 40 , and the electrolytic solution channel 30 and the fuel channel 40 were thermal compression bonded to both sides of the fuel electrode 10 .
  • the external members 14 and 24 made of the above-described material were formed, and the fuel inlet 14 A and the fuel outlet 14 B configured of, for example, joints made of a resin were arranged in the external member 14 , and the electrolytic solution inlet 24 A and the electrolytic solution outlet 24 B configured of, for example, joints made of a resin were arranged in the external member 24 .
  • the fuel electrode 10 and the oxygen electrode 20 were arranged so as to face each other so that the electrolytic solution channel 30 was arranged between the fuel electrode 10 and the oxygen electrode 20 and the fuel channel 40 was arranged outside, and the fuel electrode 10 and the oxygen electrode 20 were contained in the external members 14 and 24 . Thereby, the fuel cell 110 B illustrated in FIG. 15 was completed.
  • the fuel cell 110 B was mounted in a system including the measurement section 120 , the control section 130 , the electrolytic solution supply section 140 and the fuel supply section 150 all having the above-described configurations so as to form the fuel cell system 1 A illustrated in FIG. 8 .
  • the electrolytic solution supply adjustment section 142 and the fuel supply adjustment section 152 were configured of diaphragm type quantitative pumps (manufactured by KNF Neuberger GmbH), and the pumps were directly connected to electrolytic solution inlet 24 A and the fuel inlet 14 A through the electrolytic solution supply line 143 and the fuel supply line 153 configured of silicone tubes, respectively, and the electrolytic solution F 1 and the fuel F 2 were supplied to the electrolytic solution channel 30 and the fuel channel 40 at an arbitrary flow velocity, respectively.
  • electrolytic solution F 1 1M sulfuric acid was used, and the flow velocity was 1.0 ml/min.
  • fuel F 2 a mixed liquid of 5M methanol and 1M sulfuric acid was used, and the flow velocity was 0.080 ml/min.
  • Example 1 As Comparative Example 1 relative to the example, a fuel cell was formed as in the case of Example 4 except that the functional layer 51 was not arranged, and a fuel cell system using the fuel cell was formed.
  • Example 4 and Comparative Example 1 were connected to an electrochemical measurement system (Multistat 1480 manufactured by Solartoron Co., Ltd) to perform a constant current mode operation, and the characteristics of the fuel cell systems were evaluated. As a measurement condition, the current density was approximately 150 mA/cm 2 .
  • the result of Comparative Example 1 and the result of Example 4 are illustrated in FIGS. 30 and 31 , respectively.
  • the fuel cells operated at a current value at which the generation of CO 2 was visible, so in Comparative Example 1 in which the functional layer was not included, the influence was obvious.
  • Excess CO 2 was generated as bubbles on the electrolytic solution F 1 side, and these bubbles were not completely removed from the electrolytic solution channel 30 , and exit in the electrolytic solution channel 30 , thereby the flow of the electrolytic solution F 1 was disturbed.
  • the bubbles also affect the proton conductivity of the electrolytic solution F 1 , so as illustrated in FIG. 30 , in Comparative Example 1, characteristics were extremely unstable.
  • the voltage was reduced, and when CO 2 bubbles were transferred from the electrolytic solution channel 30 , the voltage was increased.
  • Example 4 in which the functional layer 51 was formed, it was obvious from FIG. 31 that the characteristics were extremely stable. It was considered that it was because almost all generated CO 2 was released into the fuel F 2 as bubbles. That is, it was confirmed that when the functional layer 51 was arranged on the catalyst layer 11 of the fuel electrode 10 , the direction where the carbon dioxide bubbles were released was controllable, and the characteristics were allowed to be stabilized.
  • the fuel cell 110 having the same configuration as that in FIG. 16 was formed. At that time, while the functional layer 51 was not formed in the fuel electrode 10 , a blend layer of PVDF as a water repellent resin and a polyperfluoroalkyl sulfonic acid-based resin (“Nafion (a registered trademark)” manufactured by E. I. du Pont de Nemours and Company) as a proton conductor was formed on the catalyst layer 21 of the oxygen electrode 20 as the functional layer 52 .
  • the fuel cell 110 B was formed as in the case of Example 4 except for this, and the fuel cell system 1 A was formed.
  • Example 2 As Comparative Example 2 relative to the example, a fuel cell was formed as in the case of Example 4, except that the functional layer 52 was not arranged, and a fuel cell system was formed using the fuel cell.
  • the configurations of the fuel electrode 10 , the oxygen electrode 20 , the fuel channel 30 and the electrolytic solution channel 40 are described in detail, but they may have any other configuration or may be made of any other material.
  • the fuel channel 30 may be configured of a sheet made of a porous material or the like in addition to a channel formed by processing the resin sheet described in the above-described first embodiment and examples.
  • the case where a plurality of fuel cell elements 111 are stacked in a vertical direction (a stacking direction) to form the fuel cell stack 110 is described; however, for example, as illustrated in FIG. 34 , the invention is applicable to the case where a plurality of fuel cell elements 111 are stacked in a horizontal direction (a stack plane direction) to form the fuel cell stack 110 .
  • the gas-liquid separation film 60 described in the fourth embodiment may be arranged between the fuel channel 40 and the fuel electrode 10 .
  • FIGS. 36 and 37 illustrate modification examples of the fuel channel 40 , but the same modification examples are applicable to the electrolytic solution channel 30 .
  • the rib 55 may be arranged one or more of the parallel channels 54 .
  • the heights H 1 of the ribs 55 in all of the parallel channels 54 are equal to one another is described; however, the height H 1 of the rib 55 may differ in each of the parallel channels 54 .
  • the rib 55 is arranged in a lower part of the parallel channel 54 ; however, as illustrated in FIG. 38(A) , the rib 55 may be formed in an upper part of the parallel channel 54 , or as illustrated in FIG. 38(B) , the rib 55 may be arranged in one or both of a right part and a left part of the parallel channel 54 , or as illustrated in FIG. 38(C) , the rib 55 may be formed in all of the upper, lower, right and left parts of the parallel channel 54 .
  • an electrolyte film 70 made of a polyperfluoroalkyl sulfonic acid-based resin (“Nafion (a registered trademark)” manufactured by E. I. du Pont de Nemours and Company) or any other resin having proton conductivity may be arranged between the fuel electrode 10 and the oxygen electrode 20 .
  • the gas-liquid separation film 60 described in the fourth embodiment may be arranged between the fuel channel 30 and the fuel electrode 10 .
  • the electrolytic solution F 1 circulates between the fuel cell 110 and the electrolytic solution supply section 140 ; however, the electrolytic solution F 1 may not circulate and remain stationary between the fuel electrode 10 and the oxygen electrode 20 .
  • one fuel cell 110 A is described as an example; however, the invention is applicable to a fuel cell stack in which a plurality of fuel cells 110 A are stacked in a vertical direction (a stacking direction) or a horizontal direction (a stack plane direction), and the invention is extremely effective to reduce the thickness and the size of the fuel cell stack.
  • the channel structure of the invention is applied to the fuel channel 30 and the electrolytic solution channel 40 of the fuel cell 110 A is described; however, the channel structure of the invention is widely applicable to applications for flowing a fluid through parallel channels such as a boiler, a radiator or a concentration sensor.
  • the electrolytic solution F 1 is in a state in which the electrolytic solution F 1 consistently flows during electric power generation is described; however, the invention is widely applicable to fuel cells using a liquid electrolyte such as a fuel cell using the electrolytic solution F 1 in a stationary state.
  • a fuel cell stack is configured by stacking a plurality of fuel cells 110 in a vertical direction (a stacking direction) or a horizontal direction (in a stack plane direction).
  • each component, a bonding method, electric power generation conditions in the fuel cell stack 11 and the like are not limited to those described in the above-described embodiments and examples, and any other material, any other thickness and any other bonding method may be used, and any other electric power generation conditions may be used.
  • the configurations of the fuel electrode 10 , the oxygen electrode 20 , the fuel channel 30 and the electrolytic solution channel 40 are described in detail; however, they may have any other configuration or may be made of any other material.
  • the fuel F 2 is supplied from the fuel supply section 150 to the fuel electrode 10 ; however, the fuel electrode 10 may be of a sealed type, and the fuel F 2 may be supplied as necessary.
  • the fuel F 2 may be any other liquid fuel such as ethanol or dimethyl ether in addition to methanol.
  • the electrolytic solution F 1 is not specifically limited as long as the electrolytic solution F 1 has proton (H+) conductivity, and examples of the electrolytic solution F 1 include a phosphoric acid and an ionic liquid in addition to the sulfuric acid.
  • the embodiments are not limited to a fuel cell using a liquid fuel, and is applicable to a fuel cell using a substance such as hydrogen other than a liquid fuel as a fuel.
  • air is supplied to the oxygen electrode 20 by natural ventilation; however, air may be forcefully supplied using a pump or the like. In this case, oxygen or a gas including oxygen may be supplied instead of air.
  • the fuel electrode 10 and the oxygen electrode 20 are arranged so as to face each other so that the electrolytic solution channel 30 is arranged between the fuel electrode 10 and the oxygen electrode 20 and the fuel channel 40 is arranged outside is described; however, the invention is applicable to a fuel cell system including a fuel cell with any other configuration.

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JP2007202006A JP5182473B2 (ja) 2007-08-02 2007-08-02 燃料電池スタックシステムおよび電子機器
JP2007216397A JP5182475B2 (ja) 2007-08-22 2007-08-22 燃料電池および電子機器
JP2007-216397 2007-08-22
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JP2007231562A JP4952453B2 (ja) 2007-09-06 2007-09-06 流路構造体
JP2007236647A JP5182476B2 (ja) 2007-09-12 2007-09-12 燃料電池および電子機器
JP2007-236647 2007-09-12
PCT/JP2008/063650 WO2009017150A1 (fr) 2007-08-02 2008-07-30 Système d'empilement de piles à combustible, structure de canal, pile à combustible, électrode et dispositif électronique

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